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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In Late Triassic (Norian–Rhaetian) times, the Jameson Land Basin lay at 40° N on the northern part of the supercontinent Pangaea. This position placed the basin in a transition zone between the relatively dry interior of the supercontinent and its more humid periphery. Sedimentation in the Jameson Land Basin took place in a lake–mudflat system and was controlled by orbitally forced variations in precipitation. Vertebrate fossils have consistently been found in these lake deposits (Fleming Fjord Formation), and include fishes, dinosaurs, amphibians, turtles, aetosaurs and pterosaurs. Furthermore, the fauna includes mammaliaform teeth and skeletal material. New vertebrate fossils were found during a joint vertebrate palaeontological and sedimentological expedition to Jameson Land in 2012. These new finds include phytosaurs, a second stem testudinatan specimen and new material of sauropodomorph dinosaurs, including osteologically immature individuals. Phytosaurs are a group of predators common in the Late Triassic, but previously unreported from Greenland. The finding includes well-preserved partial skeletons that show the occurrence of four individuals of three size classes. The new finds support a late Norian–early Rhaetian age for the Fleming Fjord Formation, and add new information on the palaeogeographical and palaeolatitudinal distribution of Late Triassic faunal provinces.

© 2015 IOP Publishing Ltd. The intense light scattered from metal nanoparticles sustaining surface plasmons makes them attractive for light trapping in photovoltaic applications. However, a strong resonant response from nanoparticle ensembles can only be obtained if the particles have monodisperse physical properties. Presently, the chemical synthesis of colloidal nanoparticles is the method that produces the highest monodispersion in geometry and material quality, with the added benefits of being low-temperature, low-cost, easily scalable and of allowing control of the surface coverage of the deposited particles. In this paper, novel plasmonic back-reflector structures were developed using spherical gold colloids with appropriate dimensions for pronounced far-field scattering. The plasmonic back reflectors are incorporated in the rear contact of thin film n-i-p nanocrystalline silicon solar cells to boost their photocurrent generation via optical path length enhancement inside the silicon layer. The quantum efficiency spectra of the devices revealed a remarkable broadband enhancement, resulting from both light scattering from the metal nanoparticles and improved light incoupling caused by the hemispherical corrugations at the cells' front surface formed from the deposition of material over the spherically shaped colloids.

Abstract The present study relates to the use of supercritical carbon dioxide (SCCO{\textless}inf{\textgreater}2{\textless}/inf{\textgreater}) to modify the properties of cork by incorporation of new molecules. The impact of SCCO{\textless}inf{\textgreater}2{\textless}/inf{\textgreater}processing on the morphology and on the mechanical properties was found to be negligible.The impregnation of disperse blue 14 (blue dye) on cubic shaped cork samples of 5 mm occurs progressively,is dependent of the processing conditions and of the presence of lenticels and growth rings. The impregnation of the samples bulk was achieved with processing at 10 MPa and 313 K for 16 h. The solubility and sorption of SCCO{\textless}inf{\textgreater}2{\textless}/inf{\textgreater} in the cork matrix was measured using circular discs and the diffusion coefficients calculated to be on the order of 10{\textless}sup{\textgreater}-8{\textless}/sup{\textgreater} cm{\textless}sup{\textgreater}2{\textless}/sup{\textgreater}/s, the same order as for wood materials. This work demonstrates the feasibility of supercritical fluid technology to impart new features to cork, which may lead to innovative architectural, outdoor and industrial applications.

© 2015 Elsevier B.V. Abstract Deep eutectic solvents (DES) can be formed by bioactive compounds or pharmaceutical ingredients. A therapeutic DES (THEDES) based on ibuprofen, a non-steroidal anti-inflammatory drug (NSAID), and menthol was synthesized and its thermal behavior was analyzed by differential scanning calorimetry (DSC). A controlled drug delivery system was developed by impregnating a starch:poly-Ï$μ$-caprolactone polymeric blend (SPCL 30:70) with the menthol:ibuprofen THEDES in different ratios (10 and 20 wt{%}), after supercritical fluid sintering at 20 MPa and 50 °C. The morphological characterization of SPCL matrices impregnated with THEDES was performed by scanning electron microscopy (SEM) and micro-computed tomography (micro-CT). Drug release studies were carried out in a phosphate buffered saline. The results obtained provide important clues for the development of carriers for the sustainable delivery of bioactive compounds.

We report a sol-gel approach to fabricate aluminum-oxy-hydroxide (AlOOH) -based inks for gravure printing of high-dielectric-constant nanocomposite films. By reacting 3-glycidoxypropyl- trimethoxysilane (GPTS) with aluminum-oxide-hydroxide (AlOOH) nanoparticles under constant bead milling, inks suitable for gravure printing were obtained. The calculated relative dielectric constant based on measured capacitances and film thicknesses for the gravure-printed GPTS:AlOOH nanocomposite varied between 7 and 11 at a 10 kHz frequency. The dielectric constant depended on the mixing ratio of the composite and was found to follow the Maxwell-Garnett ternary-system mixing rule indicating presence of micro/nanopores that affect the electrical properties of the fabricated films. Increasing leakage current with increasing AlOOH content was observed. High leakage current was reduced by printing two-layer films. The double-layered gravure-coated films exhibited similar capacitance density but clearly lower leakage current and less electrical breakdowns in comparison to single-layered films having comparable film compositions and film thicknesses. The best composite yielded a capacitance density of 109 ± 2 pF/mm2 at the 10 kHz frequency and a leakage current density of 60 ± 20 µA/cm2 at 0.5 MV/cm electric field as a single layer. The calculated relative dielectric constant at the 10 kHz frequency for this composition was 11.2 ± 0.5. Introduction

Transparent metal oxides thin films are a class of inorganic conductors and semiconductors with significant importance for use in portable electronics, displays, flexible electronics, multi-functional windows and solar cells. Due to the recent development of transparent and flexible electronics, there is a growing interest in depositing metal-oxide thin-film on plastic substrates that can offer flexibility, lighter weight, and potentially lead to cheaper manufacturing by allowing printing and roll- to-roll processing. The plastic substrates, however, limit device processing to below 200oC. In this context, the deposition of high-performance semiconductor thin films from dispersions of pre-prepared oxide nanoparticles at temperatures below 200oC represents a potential key route. This paper reports on the preparation of ZnO transparent thin films using solution- processed nanoparticles (NPs) precipitated from zinc acetate alcoholic solution with potassium hydroxide. The nanoparticles size distribution, microstructure and crystallinity were measured by dynamic light scattering (DLS), Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). The thin films were deposited by spin-coating onto soda lima glass substrate, using a dispersion of 1wt{%} ZnO NPs. The morphology of the films annealed at 120 and 180oC, observed by atomic force microscopy and cross-section scanning electron microscopy, shows columnar grains with diameter ranging between 20 and 70 nm, depending on the conditions of depositions. Optical measurements indicated high transparency, between 85 and 94 {%}, in the visible range, a direct nature of band-to-band transitions and band gap values between 3,22 and 3,32 eV. The refractive index and extinction coefficient have been calculated from optical transmittance and reflectance spectra.

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.

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.

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.

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.