Metal nanoparticles and diffractive nanostructures are widely studied for enhancing light trapping efficiency in thin-film solar cells. Both have achieved high performance enhancements, but there are very few direct comparisons between the two. Also, it is difficult to accurately determine the parasitic absorption of metal nanoparticles. Here, we assess the light trapping efficiencies of both approaches in an identical absorber configuration. We use a 240 nm thick amorphous silicon slab as the absorber layer and either a quasi-random supercell diffractive nanostructure or a layer of self-assembled metal nanoparticles for light trapping. Both the plasmonic and diffractive structures strongly enhance the absorption in the red/near-infrared regime. At longer wavelengths, however, parasitic absorption becomes evident in the metal nanoparticles, which reduces the overall performance of the plasmonic approach. We have formulated a simple analytical model to assess the parasitic absorption and effective reflectivity of a plasmonic reflector and to demonstrate good agreement with the experimental data.

Aerogels are a special class of ultra-light porous materials with growing interest in biomedical applications due to their open pore structure and high surface area. However, they usually lack macroporosity, while mesoporosity is typically high. In this work, carbon dioxide induced gelation followed by expansion of the dissolved CO{\textless}inf{\textgreater}2{\textless}/inf{\textgreater} was performed to produce hybrid calcium-crosslinked alginate-starch hydrogels with dual meso- and macroporosity. The hydrogels were subjected to solvent exchange and supercritical drying to obtain aerogels. Significant increase in macroporosity from 2 to 25{%} was achieved by increasing expansion rate from 0.1 to 30 bar/min with retaining mesoporosity (BET surface and BJH pore volume in the range 183-544m{\textless}sup{\textgreater}2{\textless}/sup{\textgreater}/g and 2.0-6.8cm{\textless}sup{\textgreater}3{\textless}/sup{\textgreater}/g, respectively). In vitro bioactivity studies showed that the alginate-starch aerogels are bioactive, i.e. they form hydroxyapatite crystals when immersed in a simulated body fluid solution. Bioactivity is attributed to the presence of calcium in the matrix. The assessment of the biological performance showed that the aerogels do not present a cytotoxic effect and the cells are able to colonize and grow on their surface. Results presented in this work provide a good indication of the potential of the alginate-starch aerogels in biomedical applications, particularly for bone regeneration.

Nowadays there is a strong demand for intelligent packaging to provide comfort, welfare and security to owners, vendors and consumers by allowing them to know the contents and interact with the goods. This is of particular relevance for low cost, fully disposable and recyclable products, such as identification tags and medical diagnostic tests, and devices for analysis and/or quality control in food and pharmaceutical industries. However, the increase of complexity and processing capacity requires continuous power and can be addressed by the combined use of a small disposable battery, charged by a disposable solar cell, which is able to work under indoor lighting. Herein, we show a proof-of-concept of the pioneering production of thin-film amorphous silicon (a-Si:H) solar cells with an efficiency of 4{%} by plasma enhanced chemical vapour deposition (PECVD) on liquid packaging cardboard (LPC), which is commonly used in the food and beverage industries. Such accomplishment put us one step closer to this revolution by providing a flexible, renewable and extremely cheap autonomous energy packaging system. Moreover, such Si thin films take advantage of their good performance at low-light levels, which also makes them highly desirable for cheap mobile indoor applications.

Solution-processed field-effect transistors are strategic building blocks when considering low-cost sustainable flexible electronics. Nevertheless, some challenges (e.g., processing temperature, reliability, reproducibility in large areas, and cost effectiveness) are requirements that must be surpassed in order to achieve high-performance transistors. The present work reports electrolyte-gated transistors using as channel layer gallium–indium-zinc-oxide nanoparticles produced by solvothermal synthesis combined with a solid-state electrolyte based on aqueous dispersions of vinyl acetate stabilized with cellulose derivatives, acrylic acid ester in styrene and lithium perchlorate. The devices fabricated using this approach display a ION/IOFF up to 1 × 106, threshold voltage (VTh) of 0.3–1.9 V, and mobility up to 1 cm2/(V s), as a function of gallium–indium-zinc-oxide ink formulation and two different annealing temperatures. These results validates the usage of electrolyte-gated transistors as a viable and promising alternative for nanoparticle based semiconductor devices as the electrolyte improves the interface and promotes a more efficient step coverage of the channel layer, reducing the operating voltage when compared with conventional dielectrics gating. Moreover, it is shown that by controlling the applied gate potential, the operation mechanism of the electrolyte-gated transistors can be modified from electric double layer to electrochemical doping.

The present development of non-wafer-based photovoltaics (PV) allows supporting thin film solar cells on a wide variety of low-cost recyclable and flexible substrates such as paper, thereby extending PV to a broad range of consumer-oriented disposable applications where autonomous energy harvesting is a bottleneck issue. However, their fibrous structure makes it challenging to fabricate good-performing inorganic PV devices on such substrates. The advances presented here demonstrate the viability of fabricating thin film silicon PV cells on paper coated with a hydrophilic mesoporous layer. Such layer can not only withstand the cells production temperature (150 °C), but also provide adequate paper sealing and surface finishing for the cell's layers deposition. The substances released from the paper substrate are continuously monitored during the cell deposition by mass spectrometry, which allows adapting the procedures to mitigate any contamination from the substrate. In this way, a proof-of-concept solar cell with 3.4{%} cell efficiency (41{%} fill factor, 0.82 V open-circuit voltage and 10.2 mA cm−2 short-circuit current density) is attained, opening the door to the use of paper as a reliable substrate to fabricate inorganic PV cells for a plethora of indoor applications with tremendous impact in multi-sectorial fields such as food, pharmacy and security.

Solution based deposition has been recently considered as a viable option for low-cost flexible electronics. In this context research efforts have been increasingly centred on the development of suitable solution-processed materials for oxide based transistors. Nevertheless, the majority of synthetic routes reported require the use of toxic organic solvents. In this work we report on a new environmental friendly solution combustion synthesis route, using ethanol as solvent, for the preparation of indium/gallium free amorphous zinc-tin oxide (ZTO) thin film transistors (TFTs) including AlOx gate dielectric. The decomposition of ZTO and AlOx precursor solutions, electrical characterization and stability of solution processed ZTO/AlOx TFTs under gate-bias stress, in both air and vacuum atmosphere, were investigated. The devices demonstrated low hysteresis ($Δ$V = 0.23 V), close to zero turn on voltage, low threshold voltage (VT = 0.36 V) and a saturation mobility of 0.8 cm2 V−1 s−1 at low operation voltages. Ethanol based ZTO/AlOx TFTs are a promising alternative for applications in disposable, low cost and environmental friendly electronics.

Marine sponges are extremely rich in natural products and are considered a promising biological resource. The major objective of this work is to couple a green extraction process with a natural origin raw material to obtain sponge origin collagen/gelatin for biomedical applications. Marine sponge collagen has unique physicochemical properties, but its application is hindered by the lack of availability due to inefficient extraction methodologies. Traditional extraction methods are time consuming as they involve several operating steps and large amounts of solvents. In this work, we propose a new extraction methodology under mild operating conditions in which water is acidified with carbon dioxide (CO2) to promote the extraction of collagen/gelatin from different marine sponge species. An extraction yield of approximately 50{%} of collagen/gelatin was achieved. The results of Fourier transformed infrared spectroscopy (FTIR), circular dichroism (CD), and differential scanning calorimetry (DSC) spectra suggest a mixture of collagen/gelatin with high purity, and the analysis of the amino acid composition has shown similarities with collagen from other marine sources. Additionally, in vitro cytotoxicity studies did not demonstrate any toxicity effects for three of the extracts.

{The present contribution comprehensively reviews the synthesis, structural characterization and current applications of group 13 metal complexes supported by heteroatom-bonded carbene ligands. Detailed structural analysis and comparison of the structure/reactivity trends of group 13 metal carbene species constitute the primary purpose of the present contribution. The current use and applications of this class of compounds are also discussed. In general, such adducts have been thoroughly characterized (both in solution or in the solid state) and structural data, frequently supported by theoretical investigations, provided insight into the stability/reactivity of the adducts formed. While essentially dominated by Arduengo-type NHC adducts, N- and P-bonded cyclic and acyclic carbene complexes of Al, Ga and In have also been recently described, including the recent use of ``carbon(0) ligands{''}. In general, recent developments in carbene group 13 species exploit the improved stability of the resulting metal complexes for either the isolation/characterization of unprecedented structural motifs or the production of robust group 13 metal reagents subsequently used for organic substrates functionalization or in catalysis. (C) 2014 Elsevier B.V. All rights reserved.}

{Two new Ar-BIAN Cu(II) complexes (where Ar-BIAN = bis(aryl-imino)acenaphthene) of formulations {[}CuCl2(Mes-BIAN)] (1) (Mes = 2,4,6-Me3C6H2) and {[}CuCl2(Dipp-BIAN)] (2) (Dipp = 2,6-iPr(2)C(6)H(3)) were synthesised by direct reaction of CuCl2 suspended in dichloromethane with the respective ligands Mes-BIAN (L1) and Dipp-BIAN (L2), dissolved in dichloromethane, under an argon atmosphere. Attempts to obtain these compounds by solubilising CuCl2 in methanol and adding a dichloromethane solution of the corresponding ligand, under aerobic conditions, gave also compound 1, but, in the case of L2, the Cu(I) dimer {[}CuCl(Dipp-BIAN)](2) (3) was obtained instead of compound 2. The compounds were fully characterised by elemental analyses, MALDI-TOF mass spectrometry, FT-IR, H-1 NMR and EPR spectroscopic techniques. The solid-state molecular structures of compounds 1-3 were determined by single crystal X-ray diffraction, showing the expected chelation of the Ar-BIAN ligands and two chloride ligands completing the coordination sphere of the Cu(11) centre. In the case of the complex 1, an intermediate coordination geometry around the Cu(II) centre, between square planar and tetrahedral, was revealed, while the complex 2 showed an almost square planar geometry. The structural differences and evaluation of energetic changes were rationalised by DFT calculations. Analysis of the electrochemical behaviour of complexes 1-3 was performed by cyclic voltammetry and the experimental redox potentials for Cu(II)/Cu(I) pairs have been compared with theoretical values calculated by DFT in the gas phase and in dichloromethane and methanol solutions. The complex 1 exhibited good activity in the reverse atom transfer radical polymerisation (ATRP) of styrene.}

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{Four novel Zinc-NHC alkyl/alkoxide/chloride complexes (4, 5, 9 and 9) were readily prepared and fully characterized, including X-ray diffraction crystallography for 5 and 9. The reaction of N-methyl-N-butyl imidazolium chloride (3.HCl) with ZnEt2 (2 equiv.) afforded the corresponding {[}(CNHC)ZnCl(Et)] complex (4) via a protonolysis reaction, as deduced from NMR data. The alcoholysis of 4 with BnOH led to quantitative formation of the dinuclear Zn(II) alkoxide species {[}(CNHC)ZnCl(OBn)]2 (5), as confirmed by X-ray diffraction analysis. The NMR data are in agreement with species 5 retaining its dimeric structure in solution at room temperature. The protonolysis reaction of N-(2,6-diisopropylphenyl)-N-ethyl methyl ether imidazolium chloride (8.HCl) with ZnEt2 (2 equiv.) yielded the {[}(CNHC)ZnCl(Et)] species 9. The latter was found to be reactive with CH2Cl2 in solution and to cleanly convert to the corresponding Zn(II) dichloride {[}(CNHC)ZnCl2]2 (9), whose molecular structure was also elucidated using X-ray diffractometry. Unlike Zn(II)-NHC alkoxide species 1 and 2, which contain a NHC flanked with an additional N-functional group (i.e. thioether and ether, respectively), the Zn(II) alkoxide species 5 incorporates a monodentate NHC ligand. The Zn(II) complexes 1, 2 and 5 were tested in the ring-opening polymerization (ROP) of trimethylene carbonate (TMC). All three species are effective initiators for the controlled ROP of trimethylene carbonate, resulting in the production of narrow disperse PTMC material. Initiator 1 (incorporating a thioether moiety) was found to perform best in the ROP of TMC. Notably, the latter also readily undergoes the sequential ROP of TMC and rac-LA in the presence of a chain-transfer agent, leading to well-defined and high-molecular-weight PTMC/PLA block copolymers. Copyright (c) 2014 John Wiley & Sons, Ltd.}

{Three fluorinated Mo-Cu-thiolate isomers,{[}Ph4Ph{[}S2MoS2Cu(n-SPhF)], {[}n-SPhF = 2-fluorothiophenol (la)], 3-fluorothiophenol (lb), and 4-fluorothiophenol (1c)] were synthesized and spectroscopically characterized. The F-19-NMR signal of the fluorine atom in the.benzene has different chemical shift for each isomer, which is highly influenced by the local environment that can be manipulated by different solvents and solutes. The fluorine-19 chemical shift is an advantageous NMR structural probe in alternative to H-1-NMR {[}B.K. Maiti, T. Aviles, M. Matzapetakis, I. Moura, S.R. Pauleta, JJ.G. Moura, Eur. J. Inorg. Chem. (2012) 4159.], that can be used to provide local information on the pocket of the metal cluster in the Orange Protein (ORP). (C) 2014 Elsevier B.V. All rights reserved.}

{The complex {[}Ph4P](2){[}Cu(bdt)(2)] (1(red)) was synthesized by the reaction of {[}Ph4P]2{[}S2MoS2CuCl] with H2bdt (bdt = benzene-1,2-dithiolate) in basic medium. 1(red) is highly susceptible toward dioxygen, affording the one electron oxidized diamagnetic compound {[}Ph4P]{[}Cu(bdt)(2)] (1(ox)). The interconversion between these two oxidation states can be switched by addition of O-2 or base (Et4NOH = tetraethylammonium hydroxide), as demonstrated by cyclic voltammetry and UV-visible and EPR spectroscopies. Thiomolybdates, in free or complex forms with copper ions, play an important role in the stability of 1(red) during its synthesis, since in its absence, 1(ox) is isolated. Both 1(red) and 1(ox) were structurally characterized by X-ray crystallography. EPR experiments showed that 1(red) is a Cu(II)-sulfur complex and revealed strong covalency on the copper-sulfur bonds. DFT calculations confirmed the spin density delocalization over the four sulfur atoms (76%) and copper (24%) atom, suggesting that 1(red) has a ``thiyl radical character{''}. Time dependent DFT calculations identified such ligand to ligand charge transfer transitions. Accordingly, 1(red) is better described by the two isoelectronic structures {[}Cu(I)(bdt(2), 4S(3-{*}))](2-) {[}Cu-II(bdt(2), 4S(4-))](2-). On thermodynamic grounds, oxidation of 1(red) (doublet state) leads to 1(ox) singlet state, {[}Cu-III(bd(t)2, 4S(4-))](1-).}

Domain-Specific Languages (DSLs) developers aim to narrow the gap between the level of abstraction used by domain users and the one provided by the DSL, in order to help taming the increased complexity of computer systems and real-world problems. The quality in use of a DSL is essential for its successful adoption. We illustrate how a usability evaluation process can be weaved into the development process of a concrete DSL - FlowSL - used for specifying humanitarian campaign processes lead by an international Non-Governmental Organization. FlowSL is being developed following an agile process using Model-Driven Development (MDD) tools, to cope with vague and poorly understood requirements in the beginning of the development process.

Lead is a potent toxicant associated with adverse cardiovascular effects and hypertension in children. Yet, few studies have determined if autonomic dysfunction associated with lead exposure involves brain regions which regulate autonomic responses. Central autonomic nuclei such as the nucleus tractus solitarius (NTS) and hypothalamic defence area (HDA) may be particularly sensitive to lead infiltration because they are adjacent to ventricles and areas with semi-permeable blood-brain-barriers. To understand if autonomic nuclei are sensitive to lead accumulation Wistar rats were exposed to lead from the gestational period and lead levels were quantified in brain regions that regulate arterial pressure: the NTS and the HDA. Energy dispersive X-ray fluorescence (EDXRF) was used to quantify total brain lead levels and revealed no differences between exposed and control tissues; measured values were close to the detection limit (2μg/g). Electrothermal atomic absorption spectrometry (ETAAS) was also used, which has a greater sensitivity, to quantify lead. There was ∼2.1μg/g lead in the NTS and ∼3.1μg/g lead in the HDA of exposed rats, and no lead in the control rats. There were greater lead levels in the HDA (∼50%) as compared with the NTS. Pathology studies revealed more prominent lead granules in the HDA as compared with the NTS. Increased microglia and astrocyte activation was also noted in the NTS of lead exposed rats as compared with the HDA. Regional differences in neuro-inflammatory responses likely contribute to heterogeneous lead accumulation, with enhanced clearance of lead in the NTS. Future studies will resolve the mechanisms underpinning tissue-specific lead accumulation.

Lead is a potent toxicant associated with adverse cardiovascular effects and hypertension in children. Yet, few studies have determined if autonomic dysfunction associated with lead exposure involves brain regions which regulate autonomic responses. Central autonomic nuclei such as the nucleus tractus solitarius (NTS) and hypothalamic defence area (HDA) may be particularly sensitive to lead infiltration because they are adjacent to ventricles and areas with semi-permeable blood-brain-barriers. To understand if autonomic nuclei are sensitive to lead accumulation Wistar rats were exposed to lead from the gestational period and lead levels were quantified in brain regions that regulate arterial pressure: the NTS and the HDA. Energy dispersive X-ray fluorescence (EDXRF) was used to quantify total brain lead levels and revealed no differences between exposed and control tissues; measured values were close to the detection limit (2μg/g). Electrothermal atomic absorption spectrometry (ETAAS) was also used, which has a greater sensitivity, to quantify lead. There was ∼2.1μg/g lead in the NTS and ∼3.1μg/g lead in the HDA of exposed rats, and no lead in the control rats. There were greater lead levels in the HDA (∼50%) as compared with the NTS. Pathology studies revealed more prominent lead granules in the HDA as compared with the NTS. Increased microglia and astrocyte activation was also noted in the NTS of lead exposed rats as compared with the HDA. Regional differences in neuro-inflammatory responses likely contribute to heterogeneous lead accumulation, with enhanced clearance of lead in the NTS. Future studies will resolve the mechanisms underpinning tissue-specific lead accumulation.

An integration of undoped InOx and commercial ITO thin films into laboratory assembled light shutter devices is made. Accordingly, undoped transparent conductive InOx thin films, about 100 nm thick, are deposited by radiofrequency plasma enhanced reactive thermal evaporation (rf-PERTE) of indium teardrops with no intentional heating of the glass substrates. The process of deposition occurs at very low deposition rates (0.1–0.3 nm/s) to establish an optimized reaction between the oxygen plasma and the metal vapor. These films show the following main characteristics: transparency of 87% (wavelength, λ = 632.8 nm) and sheet resistance of 52 Ω/sq; while on commercial ITO films the transparency was of 92% and sheet resistance of 83 Ω/sq. The InOx thin film surface characterized by AFM shows a uniform grain texture with a root mean square surface roughness of Rq∼2.276 nm. In contrast, commercial ITO topography is characterized by two regions: one smoother with Rq∼0.973 nm and one with big grains (Rq∼3.617 nm). For the shutters assembled using commercial ITO, the light transmission coefficient (Tr) reaches the highest value (Trmax) of 89% and the lowest (Trmin) of 1.3% [13], while for the InOx shutters these values are 80.1% and 3.2%, respectively. Regarding the electric field required to achieve 90% of the maximum transmission in the ON state (Eon), the one presented by the devices assembled with commercial ITO coated glasses is 2.41 V/μm while the one presented by the devices assembled with InOx coated glasses is smaller, 1.77 V/μm. These results corroborate the device quality that depends on the base materials and fabrication process used.

{An integration of undoped InOx and commercial ITO thin films into laboratory assembled light shutter devices is made. Accordingly, undoped transparent conductive InOx thin films, about 100 nm thick, are deposited by radiofrequency plasma enhanced reactive thermal evaporation (rf-PERTE) of indium teardrops with no intentional heating of the glass substrates. The process of deposition occurs at very low deposition rates (0.1-0.3 nm/s) to establish an optimized reaction between the oxygen plasma and the metal vapor. These films show the following main characteristics: transparency of 87% (wavelength

Os protocolos de replicação parcial de dados apresentam um grande potencial de escalabilidade. O SCORe é um protocolo para replicação parcial proposto recentemente que faz uso de controlo de concorrência multi-versão. Neste artigo abordamos um dos problemas principais que afeta o desempenho deste tipo de protocolos: a localidade dos dados, i.e., pode-se dar o caso do nó local não ter uma cópia dos dados a que pretende aceder, e nesse caso é necessário realizar uma ou mais operações de leitura remota. Assim, a não ser que se empreguem técnicas para melhorar a localidade no acesso aos dados, o número de operações de leitura remota aumenta com o tamanho do sistema, acabando por afetar o desempenho do mesmo. Nesse sentido, introduzimos um mecanismo de caching que permite replicar cópias de dados remotos de maneira a que seja poss{\'ı}vel servir localmente dados remotos enquanto que se mantém a consistência dos mesmos e a escalabilidade oferecida pelo protocolo. Avaliamos o mecanismo de caching com um benchmark conhecido da literatura e os resultados experimentais mostram resultados animadores com algum aumento no desempenho do sistema e uma redução considerável da quantidade de operações de leitura remota.