© 2015 Elsevier B.V. Ureteral stents are indispensable tools in urologic practice. The main complications associated with ureteral stents are dislocation, infection, pain and encrustation. Biodegradable ureteral stents are one of the most attractive designs with the potential to eliminate several complications associated with the stenting procedure. In this work we hypothesize the impregnation of ketoprofen, by CO 2 -impregnation in a patented biodegradable ureteral stent previously developed in our group. The biodegradable ureteral stents with each formulation: alginate-based, gellan gum-based were impregnated with ketoprofen and the impregnation conditions tested were 100 bar, 2 h and three different temperatures (35 °C, 40°C and 50°C). The impregnation was confirmed by FTIR and DSC demonstrated the amorphization of the drug upon impregnation. The in vitro elution profile in artificial urine solution (AUS) during degradation of a biodegradable ureteral stent loaded with ketoprofen was evaluated. According to the kinetics results these systems have shown to be very promising for the release ketoprofen in the first 72 h, which is the necessary time for anti-inflammatory delivery after the surgical procedure. The in vitro release studied revealed an influence of the temperature on the impregnation yield, with a higher impregnation yield at 40°C. Higher yields were also obtained for gellan gum-based stents. The non-cytotoxicity characteristic of the developed ketoprofen-eluting biodegradable ureteral stents was evaluated in L929 cell line by MTS assay which demonstrated the feasibility of this product as a medical device.

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.

This paper presents a novel approach toward the production of hybrid alginate–lignin aerogels. The key idea of the approach is to employ pressurized carbon dioxide for gelation. Exposure of alginate and lignin aqueous alkali solution containing calcium carbonate to CO2at 4.5 MPa resulted in a hydrogel formation. Various lignin and CaCO3concentrations were studied. Stable hydrogels could be formed up to 2:1 (w/w) alginate-to-lignin ratio (1.5 wt{%} overall biopolymer concentration). Upon substitution of water with ethanol, gels were dried in supercritical CO2to produce aerogels. Aerogels with bulk density in the range 0.03–0.07 g/cm3, surface area up to 564 m2/g and pore volume up to 7.2 cm3/g were obtained. To introduce macroporosity, the CO2induced gelation was supplemented with rapid depressurization (foaming process). Macroporosity up to 31.3 ± 1.9{%} with interconnectivity up to 33.2 ± 8.3{%} could be achieved at depressurization rate of 3 MPa/min as assessed by micro-CT. Young's modulus of alginate–lignin aerogels was measured in both dry and wet states. Cell studies revealed that alginate–lignin aerogels are non-cytotoxic and feature good cell adhesion making them attractive candidates for a wide range of applications including tissue engineering and regenerative medicine.

In this study, we report solution-processed amorphous zinc tin oxide transistors exhibiting high operational stability under positive gate bias stress, translated by a recoverable threshold voltage shift of about 20{%} of total applied stress voltage. Under vacuum condition, the threshold voltage shift saturates showing that the gate-bias stress is limited by trap exhaustion or balance between trap filling and emptying mechanism. In ambient atmosphere, the threshold voltage shift no longer saturates, stability is degraded and the recovering process is impeded. We suggest that the trapping time during the stress and detrapping time in recovering are affected by oxygen adsorption/desorption processes. The time constants extracted from stretched exponential fitting curves are ≈106 s and 105 s in vacuum and air, respectively.

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.

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.

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 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.

{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).

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A novel immobilized Ca0.6Ho0.4MnO3 photocatalyst has been developed with high photocatalytic activity for Rhodamine 6G (Rh6G) photodegradation under visible light irradiation. The nanocrystalline Ca0.6Ho0.4MnO3 films were successfully deposited by RF-magnetron sputtering on unheated quartz glass substrates using Ca0.6Ho0.4MnO3 powder as sputtering target and its photocatalytic functionalities have been explored. The visible-light-responsive photocatalytic activity of Ca0.6Ho0.4MnO3 films was evaluated by the photodegradation of Rh6G aqueous solutions under visible light irradiation. The reusability of Ca0.6Ho0.4MnO3 films on fresh dye samples was studied, showing an efficient reuse, without decreasing the photocatalytic decolorization efficiency. Furthermore, X-ray diffraction of the reused films did not reveal additional phases indicating high photochemical stability of the films even after reusing them in successive runs. The photocatalytic efficiency of the nanocrystalline Ca0.6Ho0.4MnO3 films was further compared with TiO2 films also produced by sputtering and the results revealed a significant improvement in photocatalytic activity over TiO2 under visible light irradiation. Almost complete photodecolorization of a 5 ppm Rh6G solution was achieved in 4 h, while only 64% of dye degradation was observed in TiO2 photoassisted process. This work provides a feasible route to fabricate high-performance immobilized ABO3-based nanomaterials, and the finding opens up a new venue for designing visible light sensitive ternary compounds for photocatalytical applications. A novel immobilized Ca0.6Ho0.4MnO3 photocatalyst has been developed with high photocatalytic activity for Rhodamine 6G (Rh6G) photodegradation under visible light irradiation. The nanocrystalline Ca0.6Ho0.4MnO3 films were successfully deposited by RF-magnetron sputtering on unheated quartz glass substrates using Ca0.6Ho0.4MnO3 powder as sputtering target and its photocatalytic functionalities have been explored. The visible-light-responsive photocatalytic activity of Ca0.6Ho0.4MnO3 films was evaluated by the photodegradation of Rh6G aqueous solutions under visible light irradiation. The reusability of Ca0.6Ho0.4MnO3 films on fresh dye samples was studied, showing an efficient reuse, without decreasing the photocatalytic decolorization efficiency. Furthermore, X-ray diffraction of the reused films did not reveal additional phases indicating high photochemical stability of the films even after reusing them in successive runs. The photocatalytic efficiency of the nanocrystalline Ca0.6Ho0.4MnO3 films was further compared with TiO2 films also produced by sputtering and the results revealed a significant improvement in photocatalytic activity over TiO2 under visible light irradiation. Almost complete photodecolorization of a 5 ppm Rh6G solution was achieved in 4 h, while only 64% of dye degradation was observed in TiO2 photoassisted process. This work provides a feasible route to fabricate high-performance immobilized ABO3-based nanomaterials, and the finding opens up a new venue for designing visible light sensitive ternary compounds for photocatalytical applications.

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 O2 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)(bdt2, 4S(3-,)*)](2-) <--> [Cu(II)(bdt2, 4S(4-))](2-). On thermodynamic grounds, oxidation of 1(red) (doublet state) leads to 1(ox) singlet state, [Cu(III)(bdt2, 4S(4-))](1-).