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.

{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-).}

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

cAMP signaling in the brain mediates several higher order neural processes. Hyperpolarization-activated cyclic nucleotide-gated (HCN) channels directly bind cAMP through their cytoplasmic cyclic nucleotide binding domain (CNBD), thus playing a unique role in brain function. Neuronal HCN channels are also regulated by tetratricopeptide repeat-containing Rab8b interacting protein (TRIP8b), an auxiliary subunit that antagonizes the effects of cAMP by interacting with the channel CNBD. To unravel the molecular mechanisms underlying the dual regulation of HCN channel activity by cAMP/TRIP8b, we determined the NMR solution structure of the HCN2 channel CNBD in the cAMP-free form and mapped on it the TRIP8b interaction site. We reconstruct here the full conformational changes induced by cAMP binding to the HCN channel CNBD. Our results show that TRIP8b does not compete with cAMP for the same binding region; rather, it exerts its inhibitory action through an allosteric mechanism, preventing the cAMP-induced conformational changes in the HCN channel CNBD.

Solution processing has been recently considered as an option when trying to reduce the costs associated to deposition under vacuum. In this context most of the research efforts have been centered in the development of the semiconductors processes nevertheless the development of the most suitable dielectrics for oxide based transistors is as relevant as the semiconductor layer itself. In this work we explore the solution combustion synthesis and report on a completely new and green route for the preparation of amorphous aluminum oxide thin films; introducing water as solvent. Optimized dielectric layers were obtained for a water based precursor solution with 0.1 M concentration and demonstrated high capacitance, 625 nF cm-2 at 10 kHz, and a permittivity of 7.1. These thin films were successfully applied as gate dielectric in solution processed gallium-zinc-tin oxide (GZTO) thin film transistors (TFTs) yielding good electrical performance such as subthreshold slope of about 0.3 V dec-1 and mobility above 1.3 cm2 V-1 s-1.

Solution processing has been recently considered as an option when trying to reduce the costs associated with deposition under vacuum. In this context, most of the research efforts have been centered in the development of the semiconductors processes nevertheless the development of the most suitable dielectrics for oxide based transistors is as relevant as the semiconductor layer itself. In this work we explore the solution combustion synthesis and report on a completely new and green route for the preparation of amorphous aluminum oxide thin films; introducing water as solvent. Optimized dielectric layers were obtained for a water based precursor solution with 0.1 M concentration and demonstrated high capacitance, 625 nF cm(-2) at 10 kHz, and a permittivity of 7.1. These thin films were successfully applied as gate dielectric in solution processed gallium-zinc-tin oxide (GZTO) thin film transistors (TFTs) yielding good electrical performance such as subthreshold slope of about 0.3 V dec(-1) and mobility above 1.3 cm(2) V(-1) s(-1).

Cotton-based nanocrystalline cellulose (NCC), also known as nanopaper, one of the major sources of renewable materials, is a promising substrate and component for producing low cost fully recyclable flexible paper electronic devices and systems due to its properties (lightweight, stiffness, non-toxicity, transparency, low thermal expansion, gas impermeability and improved mechanical properties).Here, we have demonstrated for the first time a thin transparent nanopaper-based field effect transistor (FET) where NCC is simultaneously used as the substrate and as the gate dielectric layer in an 'interstrate' structure, since the device is built on both sides of the NCC films; while the active channel layer is based on oxide amorphous semiconductors, the gate electrode is based on a transparent conductive oxide.Such hybrid FETs present excellent operating characteristics such as high channel saturation mobility (>7 cm(2) V (-1) s(-1)), drain-source current on/off modulation ratio higher than 10(5), enhancement n-type operation and subthreshold gate voltage swing of 2.11 V/decade. The NCC film FET characteristics have been measured in air ambient conditions and present good stability, after two weeks of being processed, without any type of encapsulation or passivation layer. The results obtained are comparable to ones produced for conventional cellulose paper, marking this out as a promising approach for attaining high-performance disposable electronics such as paper displays, smart labels, smart packaging, RFID (radio-frequency identification) and point-of-care systems for self-analysis in bioscience applications, among others.

abstract Vermilion red, mercury sulphide (a-HgS), was one of the most important reds in art and its use as a pigment dates back to Antiquity. In medieval Europe, it could be mined as cinnabar, or produced as vermilion by heating mercury with sulphur. This work aims to study the production of synthetic vermilion as a medieval pigment and to confirm which was the source (mineral or artificial) of the reds used in Portuguese medieval illuminations. The production of synthetic vermilion was based on the process described in the Judaeo-Portuguese medieval treatise “The book on how to make colours”, using materials and technologies as close as possible to the medieval ones. The reaction mechanism was studied by following the heating process by X-ray diffraction, and it was possible to conclude that the transformation from black cubic b-HgS into red hexagonal a-HgS is a solid-state phase transition, occurring at 235 ?C. This result is contrary to what published in technical art literature, in which this process is described as a sublimation. Moreover, Scanning Electron Microscopy evidenced a sinterization effect on the artificial vermilion, not found in medieval original samples nor in paints prepared with mineral cinnabar from Almadén (Spain). Red mercury sulphide, natural and synthetic,was then prepared as a parchment-glue paint and compared to proteinaceous red paints from 12the13th century minia- tures produced in important medieval monasteries, previously fully characterized by a multi-analytical approach (m-Energy dispersive X-ray fluorescence, m-Fourier Transform Infrared Spectroscopy, Raman microscopy). A comparative Electron probe microanalysis of the red paints point to amineral provenance for medieval vermilion found in Portuguese illuminations

The orange protein (ORP) isolated from the sulfate-reducing bacterium Desulfovibrio gigas (11.8 kDa) contains a mixed-metal sulfide cluster of the type [S2MoS2CuS2MoS2](3-) noncovalently bound to the polypeptide chain. The D. gigas ORP was heterologously produced in Escherichia coli in the apo form. Different strategies were used to reconstitute the metal cluster into apo-ORP and obtain insights into the metal cluster synthesis: (1) incorporation of a synthesized inorganic analogue of the native metal cluster and (2) the in situ synthesis of the metal cluster on the addition to apo-ORP of copper chloride and tetrathiomolybdate or tetrathiotungstate. This latter procedure was successful, and the visible spectrum of the Mo-Cu reconstituted ORP is identical to the one reported for the native protein with absorption maxima at 340 and 480 nm. The (1)H-(15)N heteronuclear single quantum coherence spectra of the reconstituted ORP obtained by strategy 2, in contrast to strategy 1, exhibited large changes, which required sequential assignment in order to identify, by chemical shift differences, the residues affected by the incorporation of the cluster, which is stabilized inside the protein by both electrostatic and hydrophobic interactions.