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2019
Cristovão, AF, Sousa D, Silvestre F, Ropio I, Gaspar A, Henriques C, Velhinho A, Baptista AC, Faustino M, Ferreira I.  2019.  Customized tracheal design using 3D printing of a polymer hydrogel: influence of UV laser cross-linking on mechanical properties. 3D Print Med. 5:12.
Cristovão, AF, Sousa D, Silvestre F, Ropio I, Gaspar A, Henriques C, Velhinho A, Baptista AC, Faustino M, Ferreira I.  2019.  Customized tracheal design using 3D printing of a polymer hydrogel: influence of UV laser cross-linking on mechanical properties. 3D Printing in Medicine. 5:12. AbstractWebsite

Background
The use of 3D printing of hydrogels as a cell support in bio-printing of cartilage, organs and tissue has attracted much research interest. For cartilage applications, hydrogels as soft materials must show some degree of rigidity, which can be achieved by photo- or chemical polymerization. In this work, we combined chemical and UV laser polymeric cross-linkage to control the mechanical properties of 3D printed hydrogel blends. Since there are few studies on UV laser cross-linking combined with 3D printing of hydrogels, the work here reported offered many challenges.

Methods
Polyethylene glycol diacrylate (PEGDA), sodium alginate (SA) and calcium sulphate (CaSO4) polymer paste containing riboflavin (vitamin B2) and triethanolamine (TEOHA) as a biocompatible photoinitiator was printed in an extrusion 3D plotter using a coupled UV laser. The influence of the laser power on the mechanical properties of the printed samples was then examined in unconfined compression stress-strain tests of 1 × 1 × 1 cm3 sized samples. To evaluate the adhesion of the material between printed layers, compression measurements were performed along the parallel and perpendicular directions to the printing lines.

Results
At a laser density of 70 mW/cm2, Young’s modulus was approximately 6 MPa up to a maximum compression of 20% in the elastic regime for both the parallel and perpendicular measurements. These values were within the range of biological cartilage values. Cytotoxicity tests performed with Vero cells confirmed the cytocompatibility.

Conclusions
We printed a partial tracheal model using optimized printing conditions and proved that the materials and methods developed may be useful for printing of organ models to support surgery or even to produce customized tracheal implants, after further optimization.

Collaço, F, Simoes SG, Dias L, Duic N, Seixas J, Bermann C.  2019.  The dawn of urban energy planning – synergies between energy and urban planning for São Paulo (Brazil) megacity. Journal of Cleaner Production. 215:458-479,doi:https://doi.org/10.1016/j.jclepro.2019.01.013.
dos Santos, R, Figueiredo C, Viecinski AC, Pina AS, Barbosa AJM, Roque ACA.  2019.  Designed affinity ligands to capture human serum albumin. Journal of Chromatography A. 1583:88-97. AbstractWebsite

Human serum albumin (HSA) in an important therapeutic agent and disease biomarker, with an increasing market demand. By proteins and drugs that bind to HSA as inspiration, a combinatorial library of 64 triazine-based ligands was rationally designed and screened for HSA binding at physiological conditions. Two triazine-based lead ligands (A3A2 and A6A5), presenting more than 50% HSA bound and high enrichment factors, were selected for further studies. Binding and elution conditions for HSA purification from human plasma were optimized for both ligands. The A6A5 adsorbent yielded a purified HSA sample with 98% purity at 100% recovery yield under mild binding and elution conditions.

Fernandes, TM, Morgado L, Salgueiro CA, Turner DL.  2019.  Determination of the magnetic properties and orientation of the heme axial ligands of PpcA from G. metallireducens by paramagnetic NMR. Journal of Inorganic Biochemistry. 198:110718. AbstractWebsite

The rising interest in the use of Geobacter bacteria for biotechnological applications demands a deep understanding of how these bacteria are able to thrive in a variety of environments and perform extracellular electron transfer. The Geobacter metallireducens bacterium can couple the oxidation of a wide range of compounds to the reduction of several extracellular acceptors, including heavy metals, toxic organic compounds or electrode surfaces. The periplasmic c-type cytochrome PpcA from this bacterium is a member of a family composed of five periplasmic triheme cytochromes, which are important to bridge the electron transfer between the cytoplasm and the extracellular environment. To better understand the functional mechanism of PpcA it is essential to obtain structural data for this cytochrome. In this work, the geometry of the heme axial ligands, as well as the magnetic properties of the hemes were determined for the oxidized form of the cytochrome, using the 13C NMR chemical shifts of the heme α-substituents. The results were further compared with those previously obtained for the homologous cytochrome from Geobacter sulfurreducens. The orientations of the axial histidine planes and the magnetic properties of the hemes are conserved in both proteins. Overall, the results obtained allowed the definition of the orientation of the magnetic axes of PpcA from G. metallireducens, which will be used as constraints to assist the solution structure determination of the cytochrome in the oxidized form.

Raminhos, J, Borges JB, Velhinho A.  2019.  Development of polymeric anepectic meshes: auxetic metamaterials with negative thermal expansion. Smart Materials and Structures. 28(4):045010. AbstractWebsite

his paper reports the application of additive manufacturing technology to fabricate bi-dimensional lightweight composite meshes capable of demonstrating auxetic properties (negative Poisson's ratio (NPR)) in combination with negative thermal expansion (NTE) behaviour, using as constituent materials polymers that do not exhibit NTE behaviour. To describe the combination of NPR and NTE characteristics, the designation of 'anepectic' is being proposed. Each mesh, obtained from varying either the material combination or the design parameters, was tested on a heated silicone bath to study the effects of the different combinations on the coefficient of thermal expansion (CTE). It was found that all meshes studied demonstrated a successful combination of NPR and NTE behaviours, and it was revealed that there is a possibility to tailor the meshes to activate the NTE behaviour within a chosen range of temperatures. For an extreme case, a Poisson's ratio of −0.056, along with a CTE of −1568 × 10−6 K−1 has been achieved.

Cordas, CM, Campaniço M, Baptista R, Maia L, Moura I, Moura JJG.  2019.  Direct electrochemical reduction of carbon dioxide by a molybdenum-containing formate dehydrogenase. J Inorg Biochem. 196:110694.Website
Esteves C, Santos GMC, Alves C, Palma S, Porteira AR, Filho J, HA C, Alves VD, Faustino BMM, Ferreira I, Gamboa H, Roque ACA.  2019.  Effect of film thickness in gelatin hybrid gels for artificial olfaction. Materials Today Bio. 1:-. AbstractPDFWebsite

Artificial olfaction is a fast-growing field aiming to mimic natural olfactory systems. Olfactory systems rely on a first step of molecular recognition in which volatile organic compounds (VOCs) bind to an array of specialized olfactory proteins. This results in electrical signals transduced to the brain where pattern recognition is performed. An efficient approach in artificial olfaction combines gas-sensitive materials with dedicated signal processing and classification tools. In this work, films of gelatin hybrid gels with a single composition that change their optical properties upon binding to VOCs were studied as gas-sensing materials in a custom-built electronic nose. The effect of films thickness was studied by acquiring signals from gelatin hybrid gel films with thicknesses between 15 and 90 μm when exposed to 11 distinct VOCs. Several features were extracted from the signals obtained and then used to implement a dedicated automatic classifier based on support vector machines for data processing. As an optical signature could be associated to each VOC, the developed algorithms classified 11 distinct VOCs with high accuracy and precision (higher than 98%), in particular when using optical signals from a single film composition with 30 μm thickness. This shows an unprecedented example of soft matter in artificial olfaction, in which a single gelatin hybrid gel, and not an array of sensing materials, can provide enough information to accurately classify VOCs with small structural and functional differences.

Esteves, C, Santos GMC, Alves C, Palma SICJ, Porteira AR, Costa HMA, Alves VD, Faustino BMM, Ferreira I, Gamboa H.  2019.  Effect of film thickness in gelatine hybrid gels for artificial olfaction. Materials Today Bio. 1:100002.
Gomes, F, Maia L, Cordas C, Moura I, Delerue-Matos C, Moura JJG, Morais S.  2019.  Electroanalytical characterization of the direct Marinobacter hydrocarbonoclasticus nitric oxide reductase-catalysed nitric oxide and dioxygen reduction. Bioelectrochem. 125:8-14.Website
Vieira, T, Silva JC, do Rego BAM, Borges JB, Henriques C.  2019.  Electrospun biodegradable chitosan based-poly(urethane urea) scaffolds for soft tissue engineering. Materials Science and Engineering: C. 103:109819. AbstractWebsite

The composition and architecture of a scaffold determine its supportive role in tissue regeneration. In this work, we demonstrate the feasibility of obtaining a porous electrospun fibrous structure from biodegradable polyurethanes (Pus) synthesized using polycaprolactone-diol as soft segment and, as chain extenders, chitosan (CS) and/or dimethylol propionic acid. Fourier transform infrared spectroscopy and proton nuclear magnetic resonance confirmed the syntheses. Fibre mats' properties were analysed and compared with those of solvent cast films. Scanning electron microscopy images of the electrospun scaffolds revealed fibres with diameters around 1 μm. From tensile tests, we found that Young's modulus increases with CS content and is higher for films (2.5 MPa to 6.5 MPa) than for the corresponding fibre mats (0.8 MPa to 3.2 MPa). The use of CS as the only chain extender improves recovery ratio and resilience. From X-ray diffraction, a higher crystalline degree was identified in fibre mats than in the corresponding films. Films' wettability was enhanced by the presence of CS as shown by the decrease of water contact angle. X-ray photoelectron spectroscopy revealed that while ester groups are predominant at the films' surface, ester and urethanes are present in similar concentrations at fibres' surface, favouring the interaction with water molecules. Both films and fibres undergo hydrolytic degradation. In vitro evaluation was performed with human dermal fibroblasts. No PU sample revealed cytotoxicity. Cells adhered to fibre mats better than to films and proliferation was observed only for samples of CS-containing PUs. Results suggest that electrospun fibres of CS-based polyurethanes are good candidate scaffolds for soft tissue engineering.

Kyprianou, I, Serghides D, Varo A, Gouveia JP, Kopeva D, Murauskaite L.  2019.  Energy Poverty Policies and Measures in 5 EU Countries: A Comparative Study.. Energy and Buildings. 196:46-60.
Gouveia, JP, Palma P, Simoes S.  2019.  Energy poverty vulnerability index: A multidimensional tool to identify hotspots for local action. . Energy Reports. 5:187-201.
Antin, K-N, Machado MA, Santos TG, Vilaça P.  2019.  Evaluation of Different Non-destructive Testing Methods to Detect Imperfections in Unidirectional Carbon Fiber Composite Ropes. Journal of Nondestructive Evaluation. 38(23) AbstractWebsite

Online monitoring of carbon fiber reinforced plastic (CFRP) ropes requires non-destructive testing (NDT) methods capable of detecting multiple damage types at high inspection speeds. Three NDT methods are evaluated on artificial and realistic imperfections in order to assess their suitability for online monitoring of CFRP ropes. To support testing, the microstructure and electrical conductivity of a carbon fiber rope is characterized. The compared methods are thermography via thermoelastic stress analysis, ultrasonic testing with commercial phased array transducers, and eddy current testing, supported by tailor-made probes. While thermoelastic stress analysis and ultrasonics proved to be accurate methods for detecting damage size and the shape of defects, they were found to be unsuitable for high-speed inspection of a CFRP rope. Instead, contactless inspection using eddy currents is a promising solution for real-time online monitoring of CFRP ropes at high inspection speeds.

Vale, T.  2019.  Executing requests concurrently in state machine replication. FCT–NOVA. (João Lourenço, Ricardo Dias, Eds.).val19.pdf
Khili, F, Borges J, Almeida PL, Boukherroub R, Omrani AD.  2019.  Extraction of Cellulose Nanocrystals with Structure I and II and Their Applications for Reduction of Graphene Oxide and Nanocomposite Elaboration. Waste and Biomass Valorization. 10:1913–1927. AbstractWebsite

The aim of the present study is to investigate the effect of the hydrolysis process on the properties of nanocrystalline cellulose (NCC) isolated from different precursors and the subsequent use of the extracted NCC for the reduction of graphene oxide (GO). The raw materials (almond and peanut shells) chosen for the isolation of cellulose were selected on the basis of their abundance and their poorly investigation in the production of NCC. Microcrystalline cellulose (MCC) was firstly extracted by alkali and bleaching treatments, then hydrolyzed under different processes to produce NCC polymorphs with structure I (NCC-I) and NCC structure II (NCC-II). The Fourier transform infrared spectroscopy, the X-ray diffraction (XRD) and the 13C NMR studies of the alkali and bleached products confirmed the formation of cellulose type I with high purity and good crystallinity, while scanning electron microscopy (SEM) showed micrometric fibers with lengths reaching 80 µm. Sulfuric acid treatment of these microfibers results in NCC type I or II, depending on the hydrolysis process. SEM of the NCC samples exhibited nanorods with diameter and aspect ratio in the range of 20–40 and 20–25 nm, respectively. Thermogravimetric analysis (TGA) of the MCC and NCC products indicated stable materials with a degradation temperature reaching 240 and 200 °C for MCC and NCC, respectively. The other part of our work concerns the use of the obtained cellulose nanocrystals (type II) for the preparation of reduced graphene oxide composite (NCC/RGO), to demonstrate the reducing properties of the isolated NCCII.

Khili, F, Borges JB, Almeida PL, Boukherroub R, Omrani AD.  2019.  Extraction of Cellulose Nanocrystals with Structure I and II and Their Applications for Reduction of Graphene Oxide and Nanocomposite Elaboration. Waste and Biomass Valorization. 10:1913-1927. AbstractWebsite

The aim of the present study is to investigate the effect of the hydrolysis process on the properties of nanocrystalline cellulose (NCC) isolated from different precursors and the subsequent use of the extracted NCC for the reduction of graphene oxide (GO). The raw materials (almond and peanut shells) chosen for the isolation of cellulose were selected on the basis of their abundance and their poorly investigation in the production of NCC. Microcrystalline cellulose (MCC) was firstly extracted by alkali and bleaching treatments, then hydrolyzed under different processes to produce NCC polymorphs with structure I (NCC-I) and NCC structure II (NCC-II). The Fourier transform infrared spectroscopy, the X-ray diffraction (XRD) and the 13C NMR studies of the alkali and bleached products confirmed the formation of cellulose type I with high purity and good crystallinity, while scanning electron microscopy (SEM) showed micrometric fibers with lengths reaching 80 µm. Sulfuric acid treatment of these microfibers results in NCC type I or II, depending on the hydrolysis process. SEM of the NCC samples exhibited nanorods with diameter and aspect ratio in the range of 20–40 and 20–25 nm, respectively. Thermogravimetric analysis (TGA) of the MCC and NCC products indicated stable materials with a degradation temperature reaching 240 and 200 °C for MCC and NCC, respectively. The other part of our work concerns the use of the obtained cellulose nanocrystals (type II) for the preparation of reduced graphene oxide composite (NCC/RGO), to demonstrate the reducing properties of the isolated NCCII.

Kiazadeh, A, Deueurmeier J.  2019.  Flexible and transparent ReRAM devices for system on panel (SOP) application. Advances in Non-Volatile Memory and Storage Technology (Second Edition). (https://doi.org/10.1016/B978-0-08-102584-0.00014-0, Ed.).:519-538., Cambridge: Woodhead-Elsevier
Castro, NSS, Laia CAT, Moura I, Carepo MS.  2019.  Fluorescence anisotropy of fluorescein varies according to pH: lessons for binding studies. J Photochem Photobiol A: Chemistry. 372:59-62.
Barbosa, AJM, Roque ACA.  2019.  Free Marine natural products databases for biotechnology and bioengineering. Biotechnology Journal. -(-):-. AbstractWebsite

Marine organisms and microorganisms are a source of natural compounds with unique chemical features. These chemical properties are useful for the discovery of new functions and applications of Marine Natural Products (MNP). To extensively exploit the potential implementations of MNPs, they are gathered in chemical databases consenting their study and screening for applications of biotechnological interest. However, classification of MNPs is currently poor in generic chemical databases. The present availability of free‐access focused MNPs databases is scarce and the molecular diversity of these databases is still very low when compared to paid‐access ones. In this review paper, the current scenario of free‐access MNP databases is presented as well as the hindrances involved in their development, mainly compound dereplication. Examples and opportunities on using freely accessible MNP databases in several important areas of biotechnology are also assessed. The scope of this paper is as well to notify the latent potential of these information sources for the discovery and development of new MNPs in biotechnology, and push future efforts to develop a public domain MNP database freely available for the scientific community.

Vilarigues, M, Coutinho I, Medici T, Alves LC, Gratuze B, Machado A.  2019.  From beams to glass: determining compositions to study provenance and production techniques. Physical Sciences Reviews. :1-24.
Ferreira, F, Ferreira I, Camacho E, Lopes F, Marques AC, Velhinho A.  2019.  Graphene oxide reinforced aluminium matrix nanostructured composited fabricated by accumulative roll bonding. Composites Part B: Engineering. 164:265-271.
Machado, C, Machado A, Palomar T, Vilarigues M.  2019.  Grisaille in Historical Written Sources. Journal of Glass Studies. 61:71-86.
Machado, MA, Antin KN, Rosado LS, Vilaça P, Santos TG.  2019.  High speed inspection of UD CFRP composites. 58th Annual Conference of the British Institute of Non-Destructive Testing, NDT 2019. , Telford, UK Abstract

Online monitoring of carbon fibre reinforced polymer (CFRP) components requires a Non-Destructive Testing (NDT) method capable of contactless sensing of damage, while enabling high inspection speeds needed for monitoring large components. Eddy current testing (ECT) of CFRP components has great potential for two reasons. First, ECT probes are capable of operating without contact, although minimizing the lift-off is preferred. Second, impedance analysers with high sample rates make high-speed inspection possible. This research assesses the damage detection capabilities of eddy current probes on CFRP samples with artificial and realistic damage. To support the aptitude of the ECT method for these needs, the CFRP material is characterized and numerical simulations are performed in order to develop optimized and tailored ECT probes for the detection of defects with different morphologies, namely fibre breakage and delaminations, and to take into consideration the highly anisotropic electrical bulk resistivity of the CFRP material. Different ECT probes were designed, produced and experimentally validated. The experiments were performed at a high inspection speed (4 m/s) and the high sensitivity of the probes was demonstrated.

Coroa, J, Morais Faustino BM, Marques AC, Bianchi C, Koskinen T, Juntunen T, Tittonen I, Ferreira I.  2019.  Highly transparent copper iodide thin film thermoelectric generator on a flexible substrate. RSC Advances. 9:35384.
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