The electronic and optical properties of p-type copper oxides (CO) strongly depend on the production technique as it influences the obtained phases: cuprous oxide (Cu2O) or cupric oxide (CuO), the most common ones. Cu films deposited by thermal evaporation have been annealed in air atmosphere, with temperature between 225 and 375 °C and time between 1 and 4 h. The resultant CO films have been studied to understand the influence of processing parameters in the thermoelectric, electrical, optical, morphological, and structural properties. Films with a Cu2O single phase are formed when annealing at 225 °C, while CuO single phase films can be obtained at 375 °C. In between, both phases are obtained in proportions that depend on the film thickness and annealing time. The positive sign of the Seebeck coefficient (S), measured at room temperature (RT), confirms the p-type behavior of both oxides, showing values up to 1.2 mV·°C–1 and conductivity up to 2.9 (Ω·m)−1. A simple detector using Cu2O have been fabricated and tested with fast finger touch events.

Mesoporous silica, SBA-15, decorated with different amounts of TiO2 (anatase) were prepared by a sol-gel method followed by hydrothermal treatment and calcination, in the presence of a soft template, copolymer Pluronic 123. Tetraethyl orthosilicate (TEOS) was used as the SiO2 precursor and commercially available TiO2 anatase nanoparticles as the supported photocatalyst. The materials were characterized by transmission electron microscopy (TEM), energy dispersive X-ray analysis (EDS), N2 adsorption-desorption isotherms, raman spectroscopy, ground state diffuse reflectance (GSDR), laser induced luminescence (LIL) and X-ray photoelectron spectroscopy (XPS). The zeta potentials of the pure SBA-15, TiO2/SBA-15 substrate and the commercial anatase sample were monitored through a complete range of pH values. All the nanomaterials developed in this work were studied in terms of their photoactivity in the UV range and in the visible range, separately. In the first case, hydroxyl radicals (OH) were confirmed to be the key active oxidizers in the photodegradation of the pesticide amicarbazone in aqueous medium. On the other hand, in the visible range, and following a dye sensitization process via a fluorescent rhodamine-like dye, two different mechanisms could be identified for the formation of the superoxide radical anion, O2−.

Heterogeneous catalysis is an exciting field in constant development. New and improved catalysts that can both be effective and economical are always on demand. Activated carbons may well play an important role in this field, as they are a cheaper alternative while more environmentally benign. In this paper, a brief overview of the effort developed in the application of activated carbon as heterogeneous catalysts in various reactions is presented. Functionalised activated carbon has been used as catalyst for fine chemical reactions. Gas-phase reactions for NO, N2O and CO2 conversions were thoroughly studied using activated carbon as catalyst support. In situ characterization techniques proved to be valuable tools to understand carbon gasification mechanism.

Rice straw (RS), rice husk (RH) and polyethylene (PE) were blended and submitted to gasification and pyrolysis processes. The chars obtained were submitted to textural, chemical, and ecotoxic characterisations, towards their possible valorisation. Gasification chars were mainly composed of ashes (73.4–89.8wt%), while pyrolysis chars were mainly composed of carbon (53.0–57.6wt%). Silicon (Si) was the major mineral element in all chars followed by alkaline and alkaline-earth metal species (AAEMs). In the pyrolysis chars, titanium (Ti) was also a major element, as the feedstock blends contained high fractions of PE which was the main source of Ti. Gasification chars showed higher surface areas (26.9–62.9m2g−1) and some microporosity, attributed to porous silica. On the contrary, pyrolysis chars did not present a porous matrix, mainly due to their high volatile matter content. The gasification bed char produced with 100% RH, at 850°C, with O2 as gasification agent, was selected for further characterization. This char presented the higher potential to be valorised as adsorbent material (higher surface area, higher content of metal cations with exchangeable capacity, and lowest concentrations of toxic heavy metals). The char was submitted to an aqueous leaching test to assess the mobility of chemical species and the ecotoxic level for V. fischeri. It was observed that metallic elements were significantly retained in the char, which was attributed mainly to its alkaline character. This alkaline condition promoted some ecotoxicity level on the char eluate that was eliminated after the pH correction.

Accepted Manuscript online November 14, 2016.The periplasmic triheme cytochrome PpcA from Geobacter sulfurreducens is highly abundant; it is the likely reservoir of electrons to the outer surface to assist the reduction of extracellular terminal acceptors; these include insoluble metal oxides in natural habitats and electrode surfaces from which electricity can be harvested. A detailed thermodynamic characterization of PpcA showed that it has an important redox-Bohr effect that might implicate the protein in e-/H+ coupling mechanisms to sustain cellular growth. This functional mechanism requires control of both the redox state and the protonation state. In the present study, isotope-labeled PpcA was produced and the three-dimensional structure of PpcA in the oxidized form was determined by NMR. This is the first solution structure of a G. sulfurreducens cytochrome in the oxidized state. The comparison of oxidized and reduced structures revealed that the heme I axial ligand geometry changed and there were other significant changes in the segments near heme I. The pH-linked conformational rearrangements observed in the vicinity of the redox-Bohr center, both in the oxidized and reduced structures, constitute the structural basis for the differences observed in the pKa values of the redox-Bohr center, providing insights into the e-/H+ coupling molecular mechanisms driven by PpcA in G. sulfurreducens.EET, extracellular electron transfer; IM, inner membrane; IPTG, isopropyl β-d-thiogalactoside; MFCs, microbial fuel cells; NOE, Nuclear Overhauser effect; OM, outer membrane; rmsd, root mean square deviation.

Aldehyde oxidases (AOXs) are molybdo-flavoenzymes characterized by broad substrate specificity, oxidizing aromatic/aliphatic aldehydes into the corresponding carboxylic acids and hydroxylating various heteroaromatic rings. Mammals are characterized by a complement of species-specific \{AOX\} isoenzymes, that varies from one in humans (AOX1) to four in rodents (AOX1, AOX2, \{AOX3\} and AOX4). The physiological function of mammalian \{AOX\} isoenzymes is unknown, although human \{AOX1\} is an emerging enzyme in phase-I drug metabolism. Indeed, the number of therapeutic molecules under development which act as \{AOX\} substrates is increasing. The recent crystallization and structure determination of human \{AOX1\} as well as mouse \{AOX3\} has brought new insights into the mechanisms underlying substrate/inhibitor binding as well as the catalytic activity of this class of enzymes.

Adsorption of model systems of triclosan by mineral sorbent diatomite is studied. The triclosan equilibrium concentration was measured spectrophotometrically, the morphology of the diatomite characterized using scanning electron microscopy and the amount of the adsorbed triclosan on the diatomite quantified by a mass balance. Adsorption isotherms were analyzed according to the linear/nonlinear form of Langmuir, Freundlich, Sips and Toth isotherm models isotherms, using AMPL software. It is shown that nonlinear Langmuir and Sips isotherm model provided suitable fitting results and no pronounced difference in adsorption efficiency between isotherms measured after 1, 2 and 3days adsorption was observed. Determined maximum adsorption capacity of diatomite towards triclosan qs is 140mg/g. Averaged calculated values of ΔG are −9.9 and −9.6kJ/mol for Langmuir and Sips models respectively. The negative sign of such values indicates spontaneous, physical in nature adsorption.

Exosomes are nanovesicles formed in the endosomal pathway with an important role in paracrine and autocrine cell communication. Exosomes secreted by cancer cells, malicious exosomes, have important roles in tumor microenvironment maturation and cancer progression. The knowledge of the role of exosomes in tumorigenesis prompted a new era in cancer diagnostics and therapy, taking advantage of the use of circulating exosomes as tumor biomarkers due to their stability in body fluids and targeting malignant exosomes’ release and/or uptake to inhibit or delay tumor development. In recent years, nanotechnology has paved the way for the development of a plethora of new diagnostic and therapeutic platforms, fostering theranostics. The unique physical and chemical properties of gold nanoparticles (AuNPs) make them suitable vehicles to pursuit this goal. AuNPs’ properties such as ease of synthesis with the desired shape and size, high surface:volume ratio, and the possibility of engineering their surface as desired, potentiate AuNPs’ role in nanotheranostics, allowing the use of the same formulation for exosome detection and restraining the effect of malicious exosomes in cancer progression.

The cooperative assembly of biopolymers and small molecules can yield functional materials with precisely tunable properties. Here, the fabrication, characterization, and use of multicomponent hybrid gels as selective gas sensors are reported. The gels are composed of liquid crystal droplets self-assembled in the presence of ionic liquids, which further coassemble with biopolymers to form stable matrices. Each individual component can be varied and acts cooperatively to tune gels' structure and function. The unique molecular environment in hybrid gels is explored for supramolecular recognition of volatile compounds. Gels with distinct compositions are used as optical and electrical gas sensors, yielding a combinatorial response conceptually mimicking olfactory biological systems, and tested to distinguish volatile organic compounds and to quantify ethanol in automotive fuel. The gel response is rapid, reversible, and reproducible. These robust, versatile, modular, pliant electro-optical soft materials possess new possibilities in sensing triggered by chemical and physical stimuli.

Alkoxylation of α−pinene, β−pinene and limonene was performed in the presence of SBA-15-occluded tungstophosphoric acid (HPW). The HPW was immobilised in SBA-15 using the sol-gel method. The catalysts were characterised by N2 adsorption, FT-IR, Raman spectroscopy, X-Ray diffraction, ICP-AES and TEM. A series of catalysts with different heteropolyacid loadings ranging from 1.8 to 19.3 wt. % were prepared. PW4-SBA-15 (with 10.8 wt. %) exhibited the highest catalytic activity for the alkoxylation of α-pinene with ethanol. An approximately 53% selectivity to α-terpinyl ethyl ether was observed over the PW-SBA-15 catalysts. PW4-SBA-15 was also used as a catalyst for the alkoxylation of other terpenes, including β-pinene and limonene. The PW4-SBA-15 catalyst exhibited high catalytic stability for the alkoxylation of α-pinene with ethanol. PW4-SBA-15 was also used as a catalyst for the esterification of free fatty acids (i.e., palmitic, stearic and oleic acids) with ethanol. Good catalytic activity was observed for the PW4-SBA-15 catalyst with the different substrates used in the esterifications.

The potential of a bacterial exopolysaccharide named FucoPol, produced by the bacterium Enterobacter A47, as encapsulation matrix was explored. Spherical capsules with a smooth surface were produced by spray drying. The obtained microcapsules had average diameters ranging from 0.5 to 26.7μm and presented thin walls (thickness from 222 to 1094nm). The capsules were loaded with two bioactive compounds: gallic acid (GA) and oregano essential oil (OEO). Both bioactive materials were encapsulated in FucoPol particles, retaining their antioxidant activity after the drying process. Release studies showed that GA release in simulated gastric and intestinal fluids was faster than that of OEO, envisaging that the latter had established stronger interactions with the polymer matrix. These results suggest that FucoPol has a good potential for use as encapsulating material of bioactive compounds for application in several areas, including food, cosmetic or pharmaceutical products.

Change is happening at an ever faster rate today, driven partly by technological changes leading to changes in all other areas of our lives. Today’s global trends, uncertainties, and surprises have the potential to significantly change the way the world works tomorrow. Shaping the world we want to live in means being more aware of the future and seeking better approaches. In such increasingly uncertain environment, planning uncertainties force policy and decision makers to foster future-oriented technology analyses (FTA) by using foresight methodologies. FTA can help us react on the likely directions of technologies, manage the risks involved and shape technological trajectories in order to improve the long term benefits to society. Foresight methodologies seek to gather data and make sense of it so that people can think in different and new ways about the future. That data might be collected from humans or from the analysis of documents and artefacts, or both. The data might be analysed using qualitative or quantitative techniques, or both. To be used in strategy processes, however, data needs to be analysed, interpreted and used in ways that make sense to the organisation. There is no single set of methods used in all foresight activities. The methods used need to reflect the resources available and the objectives of the exercise. The choice of methods is critical, though it often appears to be based upon what is fashionable or which practitioners have experience in. The methods may be organised and interrelated in different ways. In other terms, the conduct of foresight analyses needs to be tailored to the type. The first thing to do is to choose the right methods which are most appropriate to the analysis and technology characteristics. One of the substantial advances has been a move away from a tool or method driven approach to one which relies on the selection of tools in accord with their appropriateness for the particular issue being examined, their relative strengths and limitations. Thus, the experience of observing so many developing nations attempting to conduct a Japanese style Delphi survey, with an extremely limited number of ‘experts’ and doubtful relevance of estimated technology realisation times to their economy, indicates the need to develop foresight appropriate to local conditions. Their use and contribution will be determined primarily by the values, structures and cultures of the organisations applying them. This paper will try to discuss the importance of future oriented technology analysis, in particularly technology foresight, and the question of how to select the best methodology among the existing ones. Although this paper intends to lay a framework and cover the tools used in technology futures analysis, in particularly emerging air transportation technologies, a full understanding of each of these tools is out of this paper. The conduct of analysis needs to be tailored to the type. The first thing to do is to choose the right tools which are most appropriate to the analysis and the technology characteristics. Thus, we have to set the criteria and figure out key aspects and factors for designing our research. In our case, the key aspects and factors are: it is a long term vision for 10-15 years later; an emerging air transportation mode; a socio- technological system of systems in transportation area which is composed of resources and stakeholders network, drivers and disruptors; and also normative, both qualitative and quantitative, national and global. The probably research tools that can be used are; agent based modelling, cost benefit analysis, scenarios, impact analysis, case study (Visioning), subjective judgement, roadmap, interviews, benefit visualization tool, literature reviews, and attending conferences.

The xanthine oxidase (XO) family comprises molybdenum-dependent enzymes that usually form homodimers (or dimers of heterodimers/trimers) organized in three domains that harbor two [2Fe-2S] clusters, one FAD, and a Mo cofactor. In this work, we crystallized an unusual member of the family, the periplasmic aldehyde oxidoreductase PaoABC from Escherichia coli. This is the first example of an E. coli protein containing a molybdopterin-cytosine-dinucleotide cofactor and is the only heterotrimer of the XO family so far structurally characterized. The crystal structure revealed the presence of an unexpected [4Fe-4S] cluster, anchored to an additional 40 residues subdomain. According to phylogenetic analysis, proteins containing this cluster are widely spread in many bacteria phyla, putatively through repeated gene transfer events. The active site of PaoABC is highly exposed to the surface with no aromatic residues and an arginine (PaoC-R440) making a direct interaction with PaoC-E692, which acts as a base catalyst. In order to understand the importance of R440, kinetic assays were carried out, and the crystal structure of the PaoC-R440H variant was also determined.

The present work reports charging effects and surface potential variations in pure copper, cuprous oxide and cupric oxide nanowires observed by electrostatic force microscopy (EFM) and Kelvin probe force microscopy (KPFM). The copper nanowires were produced by wet synthesis, oxidation into cuprous oxide nanowires was achieved through microwave irradiation and cupric oxide nanowires were obtained via furnace annealing in atmospheric conditions. Structural characterization of the nanowires was carried out by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and energy dispersive X-ray spectroscopy. During the EFM experiments the electrostatic field of the positive probe charged negatively the Cu-based nanowires, which in turn polarized the SiO2 dielectric substrate. Both the probe/nanowire capacitance as well as the substrate polarization increased with the applied bias. Cu2O and CuO nanowires behaved distinctively during the EFM measurements in accordance with their band gap energies. The work functions (WF) of the Cu-based nanowires, obtained by KPFM measurements, yielded WFCuO {\textgreater} WFCu {\textgreater} WFCu2O.

BACKGROUND: Gold-nanobeacons (Au-nanobeacons) have proven to be versatile systems for molecular diagnostics and therapeutic actuators. Here, we present the development and characterization of two gold nanobeacons combined with Förster resonance energy transfer (FRET) based spectral codification for dual mode sequence discrimination. This is the combination of two powerful technologies onto a single nanosystem.RESULTS: We proved this concept to detect the most common fusion sequences associated with the development of chronic myeloid leukemia, e13a2 and e14a2. The detection is based on spectral shift of the donor signal to the acceptor, which allows for corroboration of the hybridization event. The Au-nanobeacon acts as scaffold for detection of the target in a homogenous format whose output capability (i.e. additional layer of information) is potentiated via the spectral codification strategy.CONCLUSIONS: The spectral coded Au-nanobeacons permit the detection of each of the pathogenic fusion sequences, with high specificity towards partial complementary sequences. The proposed BioCode Au-nanobeacon concept provides for a nanoplatform for molecular recognition suitable for cancer diagnostics.

Lung cancer is the leading cause of cancer-related mortality in the world, non-small lung cancer (NSCLC) is the most frequent subtype (85% of the cases). Within this subtype, adenocarcinoma and squamous cell carcinoma are the most frequent. New therapeutic strategies based on targeted delivery of drugs have relied on the use of biomarkers derived from the patients’ molecular profiling. Several biomarkers have been found to be useful for use as targets for precision therapy in NSCLC, such as mutations in the epidermal growth factor receptor, v-Ki-ras2 Kirsten rat sarcoma viral oncogene homolog, anaplastic lymphoma kinase, mesenchymal-epithelial transition factor receptor tyrosine kinase, BRAF, c-ros oncogene 1, P53 and phosphatase with tensin homology. Current developments in Nanomedicine have allowed for multifunctional systems capable of delivering therapeutics with increased precision to the target site/tissue, while simultaneously assisting in diagnosis. Here, we review the use of biomarkers in nanotechnology translation in NSCLC management.

The thermoelectric (TE) properties of vanadium pentoxide (V2O5) alloyed with graphite (G) were studied as a function of its incorporation percentage. Variable weight percentages of graphite powder (0–50{%}) were added to V2O5 powder and their mixtures were evaporated by a thermal evaporation technique to form thin films with a thickness in the range of 30–80 nm. In the infrared wavelength region, the transmittance of the obtained films increased as the G percentage was increased, while in the visible range, it decreased with G up to 10{%}. The TE properties were improved when G was in the range of 10–30{%}, while it decreased for the other percentages: Seebeck coefficient (S) changed from 0.6 mV/K to 0.9 mV/K and was zero with a G of 50{%}; the electrical conductivity varied slightly from 5 ($Ømega$m)−1 to 0.7 ($Ømega$m)−1 while the mobility improved from 0.07 cm2/V s to 1.5 cm2/V s and the respective carrier concentration was reduced, from 1 × 1018 cm−3 to 4 × 1016 cm−3. These films were applied as temperature sensors evaluating the thermovoltage as a function of thermal gradient between two electrodes, in which one was maintained at room temperature.

Oxidized and sulfonated-activated carbons (AC) were tested in the catalytic conversion of glycerol by acetalization reactions. The solids were treated with concentrated nitric acid and/or fuming sulfuric acid (AC, AC-N, AC-S, and AC-NS). The presence of sulfur and an increase in the acidity of the solids demonstrate the suitability of the oxidation as well as the sulfonation process, especially in the sample treated with concentrated nitric acid and fuming sulfuric acid (AC-NS). The best catalyst for the reaction of glycerol acetalization with phenylacetaldehyde was AC-NS, with a phenylacetaldehyde conversion of 95 {%} after 90 min at 383 K and selectivity of 88 and 12 {%}, respectively, to dioxolane and dioxane. These products can be used as hyacinth fragrance flavoring compounds. Furthermore, a contribution of homogeneous catalysis in these systems was not identified. Thus, we identified a possibility of glycerol conversion, a biodiesel by-product, into value-added products by suitable catalysts produced from activated carbons.

Tin complexes demonstrate antiproliferative activities in some case higher than cisplatin, with IC50 at the low micromolar range. We have previously showed that the cyclic trinuclear complex of Sn(IV) bearing an aromatic oximehydroxamic acid group [nBu(2)Sn(L)](3) (L=N,2-dihydroxy-5-[N-hydroxyethanimidoyl]benzamide) (MG85) shows high anti-proliferative activity, induces apoptosis and oxidative stress, and causes destabilization of tubulin microtubules, particularly in colorectal carcinoma cells. Despite the great efficacy towards cancer cells, this complex still shows some cytotoxicity to healthy cells. Targeted delivery of this complex specifically towards cancer cells might foster cancer treatment.MG85 complex was encapsulated into liposomal formulation with and without an active targeting moiety and cancer and healthy cells cytotoxicity was evaluated.Encapsulation of MG85 complex in targeting PEGylated liposomes enhanced colorectal carcinoma (HCT116) cancer cell death when compared to free complex, whilst decreasing cytotoxicity in non-tumor cells. Labeling of liposomes with Rhodamine allowed assessing internalization in cells, which showed significant cell uptake after 6 h of incubation. Cetuximab was used as targeting moiety in the PEGylated liposomes that displayed higher internalization rate in HCT116 cells when compared with non-targeted liposomes, which seems to internalize via active binding of Cetuximab to cells.The proposed formulation open new avenues in the design of innovative transition metal-based vectorization systems that may be further extended to other novel metal complexes towards the improvement of their anti-cancer efficacy, which is usually hampered by solubility issues and/or toxicity to healthy tissues.