In the last two decades, it has been observed an increasing low enrolment of students in chemistry teaching courses in secondary schools. On the one hand, because of the negative connotation of chemistry, associated with the potentially toxic and pollutant chemical industry, and on the other hand, that the teaching of this subject is exclusively carried out only in a theoretical classroom environment with almost non-existent practical/experimental component, despite chemistry is an experimental science in its essence. This state of affairs has been reflected in chemistry degrees offered by Portuguese universities throughout the country, which in the application process for each academic year, ended up by never completely fulfilling the number of offered nunerus clausus. Considering that the pedagogical mission of the Faculty of Science and Technology of Universidade NOVA de Lisboa (FCT-NOVA), in particular its Department of Chemistry (DQ), aims to contribute to the human, scientific and technical development of students, a project has been settled in the last nine years in order to offer to high school students a unique opportunity to arouse in them the interest in Science in general and Chemistry in particular, to stimulate impart on them the joy of curiosity, while at the same time conferring the necessary skills for their future activity as students of higher education or in the labour market. It is also through the close contact with students that method, discipline, and intellectual honesty are transmitted and cultivated. The aim of this Project was thus to promote the study and taste interest for Chemistry, through experimental activities, fitting the Portuguese High School Education curricula, offered to students enrolled in Chemistry subjects attending the 10th, 11th and 12th grades (the latter, compulsory high school degree to apply to University Throughout 2016/17 academic year, DQ-FCT-NOVA will receive, from October to May, 1888 students visits from eleven High Schools distributed among Physical Chemistry for 10th/11th grade and of the 12th grade attending the Chemistry subject. The former are offer one single laboratory activity while the latter participate up to 10 different experimental activities. During 70 practical sessions of 2.5 hours each, with an average attendance of 27 students, the number of higher education school staff involved are 22. Each high school class is accompanied by 1 teacher, who's also proactively contributing to the design of the practical session. The session is carried out in groups of 2/3 students, and the laboratories have a capacity of 24/48 according onto classes sizes. A quality questionnaire is filled by the students in order to monitor the action. In 2015/16, 63 % of the students answered the questionnaire in which more than 90% students were very satisfied with the action. This project has already been implemented for 9 years reflecting a growing collaboration between FCT-NOVA and in High Schools in the vicinity (Setubal District). Above all, this Project allowed most of these schools to continue to motivate students to enrol in 12th grade Chemistry subject. Actually, in the first year of the initiative, many of these schools did not have enough students to open chemistry classes for the 12th grade. After the first initiative, almost all high schools have been able to maintain open 12th grade chemistry classes. On the other hand, FCT-NOVA, namely, the Applied Chemistry course, has been able to fill 100% of the numerus clausus available in the first phase of the application period, which is not the case for other higher education schools courses in Portugal for the same domain - Chemistry.

Spacer-less RED stacks using membranes with integrated spacer profiles have been investigated during the last years to eliminate the spacer shadow effect. The presence of spacers partially blocks the membrane surface and creates a tortuous and thus longer path for ions in the channel, meaning higher ohmic resistance. Consequently, power outputs are reduced. Profiled membranes may solve this problem as they provide flow channels for the feed streams, while the relief formed on their surfaces keeps the membranes separated. Although the geometry and arrangement of so far used profiles led to lower ohmic resistance, it did not grant an efficient fluid mixing. Recently, so-called chevron profiles, with enhanced mixing, were proposed based on computational fluid dynamics (CFD) simulations. In the present study, the performance of such chevron-profiled membranes, prepared by thermal pressing, was experimentally validated in a reverse electrodialysis (RED) stack. According to the obtained experimental values of non-ohmic resistance and total pressure drop across the RED stack, the chevron-profiled membranes assure efficient fluid mixing at comparatively low hydraulic losses. The net power density obtained with chevron-profiled membranes was the highest obtained for the present stack design. It outperformed the alternative RED stack configurations investigated in this study, such as channels with optimized spacers and channels formed by pillar-profiled membranes. To allow for an even more straightforward and efficient RED stack assembling with chevron-profiled membranes, recommendations for a further simplified design, consisting of diagonal ridges that are assembled perpendicularly, are provided.

Accepted Manuscript online January 16, 2017.Geobacter bacteria usually prevail among other microorganisms in soils and sediments where Fe(III) reduction has a central role. This reduction is achieved by extracellular electron transfer (EET), where the electrons are exported from the interior of the cell to the surrounding environment. Periplasmic cytochromes play an important role in establishing an interface between inner and outer membrane electron transfer components. In addition, periplasmic cytochromes, in particular nanowire cytochromes that contain at least 12 haem groups, have been proposed to play a role in electron storage in conditions of an environmental lack of electron acceptors. Up to date, no redox partners have been identified in Geobacter sulfurreducens, and concomitantly, the EET and electron storage mechanisms remain unclear. In this work, NMR chemical shift perturbation measurements were used to probe for an interaction between the most abundant periplasmic cytochrome PpcA and the dodecahaem cytochrome GSU1996, one of the proposed nanowire cytochromes in G. sulfurreducens. The perturbations on the haem methyl signals of GSU1996 and PpcA showed that the proteins form a transient redox complex in an interface that involves haem groups from two different domains located at the C-terminal of GSU1996. Overall, the present study provides for the first time a clear evidence for an interaction between periplasmic cytochromes that might be relevant for the EET and electron storage pathways in G. sulfurreducens.1D, one-dimensional; CbcL, c- and b-type cytochrome for low potential; EET, extracellular electron transfer; HP, His-patch; ImcH, inner membrane c-type cytochrome; MacA, metal-reduction-associated cytochrome; NaPi, sodium phosphate; NBAF, acetate-fumarate medium; NMR, nuclear magnetic resonance; PpcA, periplasmic c-type cytochrome; SDS–PAGE, sodium dodecyl sulphate–polyacrylamide gel electrophoresis; STC, small tetrahaem cytochrome.

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.

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.

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.

During the course of evolution, the cellulosome, one of Nature's most intricate multi-enzyme complexes, has been continuously fine-tuned to efficiently deconstruct recalcitrant carbohydrates. To facilitate the uptake of released sugars, anaerobic bacteria use highly ordered protein-protein interactions to recruit these nanomachines to the cell surface. Dockerin modules located within a non-catalytic macromolecular scaffold, whose primary role is to assemble cellulosomal enzymatic subunits, bind cohesin modules of cell envelope proteins, thereby anchoring the cellulosome onto the bacterial cell. Here we have elucidated the unique molecular mechanisms used by anaerobic bacteria for cellulosome cellular attachment. The structure and biochemical analysis of five cohesin-dockerin complexes revealed that cell surface dockerins contain two cohesin-binding interfaces, which can present different or identical specificities. In contrast to the current static model, we propose that dockerins utilize multivalent modes of cohesin recognition to recruit cellulosomes to the cell surface, a mechanism that maximises substrate access while facilitating complex assembly.

The remarkable physicochemical properties of gold nanoparticles (AuNPs) have prompted developments in the exploration of biomolecular interactions with AuNP-containing systems, in particular for biomedical applications in diagnostics. These systems show great promise in improving sensitivity, ease of operation and portability. Despite this endeavor, most platforms have yet to reach maturity and make their way into clinics or points of care (POC). Here, we present an overview of emerging and available molecular diagnostics using AuNPs for biomedical sensing that are currently being translated to the clinical setting.

The limitations of platinum complexes in cancer treatment have motivated the extensive investigation into other metal complexes such as ruthenium. We herein present the synthesis and characterization of a new family of ruthenium compounds 1a–5a with the general formula [Ru(bipy)2L][CF3SO3]2 (bipy = 2,2′-bipyridine; L = bidentate ligand: N,N; N,P; P,P; P,As) which have been characterized by elemental analysis, ES-MS, 1H and 31P–{1H} NMR, FTIR and conductivity measurements. The molecular structures of four Ru(II) complexes were determined by single crystal X-ray diffraction. All compounds displayed moderate cytotoxic activity in vitro against human A2780 ovarian, MCF7 breast and HCT116 colorectal tumor cells. Compound 5a was the most cytotoxic compound against A2780 and MCF7 tumor cells with an IC50 of 4.75 ± 2.82 μM and 20.02 ± 1.46 μM, respectively. The compounds showed no cytotoxic effect on normal human primary fibroblasts but rather considerable selectivity for A2780, MCF7 and HCT116 tumor cells. All compounds induce apoptosis and autophagy in A2780 ovarian carcinoma cells and some nuclear DNA fragmentation. All compounds interact with CT-DNA with intrinsic binding constants in the order 1a > 4a > 2a > 3a > 5a. The observed hyperchromic effect may be due to the electrostatic interaction between positively charged cations and the negatively charged phosphate backbone at the periphery of the double helix-CT-DNA. Interestingly, compound 1a shows a concentration dependent DNA double strand cleavage. In addition in vivo toxicity has been evaluated on zebrafish embryos unveiling the differential toxicity between the compounds, with LC50 ranging from 8.67 mg L−1 for compound 1a to 170.30 mg L−1 for compound 2a.

The pH-sensitive affinity pair composed by neutravidin and iminobiotin was used to develop a multilayered Magnetic Resonance Imaging (MRI) nanoprobe responsive to the acidic pH of tumor microenvironment. The multilayer system was assembled on meso-2,3-dimercaptosuccinic acid-coated iron oxide magnetic nanoparticles (MNP), which convey negative MRI contrast enhancement properties to the nanoprobe. The outer stealth PEG-layer is altered in acidic media due to the disruption of interactions between neutravidin-iminobiotin. As a consequence, the positively charged inner layer is exposed and enhances interactions with cells. The nanoprobe uptake by HCT116 cells cultured in vitro under acidic conditions had a 2-fold increase compared to the uptake at physiological pH. The uptake difference is particularly clear in T2-weighted MRI phantoms of cells incubated with the nanoprobes at both pH conditions. This work sets the proof-of-concept of a MNP-based MRI nanoprobe targeting acidic tumor microenvironment through the use of a specific bio-recognition interaction that is pH-sensitive. This tumor targeting strategy is potentially applicable to the generality of tumors since the typical hypoxic conditions and high glycolysis rate in cancer cells create an acidic environment common to the majority of cancer types.