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2019
Gomes, S, Querido D, Ferreira JL, Borges JB, Henriques C, Silva JC.  2019.  Using water to control electrospun Polycaprolactone fibre morphology for soft tissue engineering. Journal of Polymer Research. 26:222. AbstractWebsite

Control of the properties of electrospun polycaprolactone can be achieved by adjusting the acetic acid:water ratio used to dissolve and electrospin the polymer. In this work, we studied the effect of using up to 15 wt% water in the solvent mixture. Solution conductivity and viscosity and fibre morphology vary dramatically with water content and solution age. Two days after initial solution preparation, electrospinning yields regular fibres for a water content of 0 wt% and 5 wt%, irregular fibres for a 10 wt% water content and irregular and fused fibres for a 15 wt% water content. Fibres with the highest crystallinity (60%) were obtained from solutions containing 5 wt% water while the highest elastic modulus (8.6 ± 1.4 MPa) and tensile stress (4.3 ± 0.3 MPa) pertain to fibres obtained from solutions containing 10 wt% water. Enzymatic fibre degradation is faster the higher the water content in the precursor solution. Adhesion ratio of human foetal fibroblasts was highest on scaffolds obtained from precursor solutions containing 0 wt% water. Cell population increases for all scaffolds and populations quickly become equivalent, with no statistically significant differences between them. Cells exhibit a more extended morphology on the 5 wt% scaffold and a more compact morphology on the 0 wt% scaffold. In summary, a small water content in the solvent allows a significant control over fibre diameter, scaffold properties and the production of scaffolds that support cell adhesion and proliferation. This strategy can be used in soft tissue engineering to influence cell behaviour and the degradation rate of the scaffolds.

Ambrosi, E, Bartlett P, Berg AI, Brivio S, Burr G, Deswal S, Deuermeier J, Haga M-A, Kiazadeh A, Kissling G, Kozicki M, Foroutan-Nejad C, Gale E, Gonzalez-Velo Y, Goossens A, Goux L, Hasegawa T, Hilgenkamp H, Huang R, Ibrahim S, Ielmini D, Kenyon AJ, Kolosov V, Li Y, Majumdar S, Milano G, Prodromakis T, Raeishosseini N, Rana V, Ricciardi C, Santamaria M, Shluger A, Valov I, Waser R, Stanley Williams R, Wouters D, Yang Y, Zaffora A.  2019.  Electrochemical metallization ReRAMs (ECM) - Experiments and modelling: General discussion. Faraday Discussions. 213:115-120. AbstractWebsite
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Sanchez-Sobrado, O, Mendes MJ, Haque S, Mateus T, Aguas H, Fortunato E, Martins R.  2019.  Lightwave trapping in thin film solar cells with improved photonic-structured front contacts. J. Mater. Chem. C. 7:6456-6464.: The Royal Society of Chemistry AbstractWebsite

Photonic microstructures placed at the topside of photovoltaic cells are currently one of the preferred light management solutions to obtain efficiency enhancement due to the increment of the optical absorption produced in the active medium of the devices. Herein{,} we present the results concerning a practical{,} low-cost and scalable approach to integrate metal-oxide based light trapping microstructures on the front contact of amorphous silicon thin film solar cells. A colloidal lithography method was used to pattern the wavelength-sized pyramidal-like features composing the structures{,} made of two different transparent materials{,} TiO2 and IZO{,} allowing the detailed study of the influence of their geometrical parameters on the optoelectronic properties of the devices. These top coating structures are deposited as a post-process after the solar cell fabrication{,} thus facilitating and broadening their industrial applicability. Measurements of the light absorption{,} external quantum efficiency and I–V curves revealed that the structured coatings provide strong broadband improvements in the generated current{,} due to the suppression of reflected light at short wavelengths and the increment of the optical path length of the longer wavelengths (via light scattering){,} within the amorphous silicon layer. As a result{,} in the four types of structures analyzed in this study{,} remarkable increments were achieved in the cells’ efficiencies (up to 14.4%) and generated currents (up to 21.5%){,} with respect to the flat reference cells.

Alexandre, M, Chapa M, Haque S, Mendes MJ, Águas H, Fortunato E, Martins R.  2019.  Optimum Luminescent Down-Shifting Properties for High Efficiency and Stable Perovskite Solar Cells. ACS Applied Energy Materials. 2:2930-2938., Number 4 AbstractWebsite

In recent years, the discovery of the excellent optical and electrical properties of perovskite solar cells (PSCs) made them a main focus of research in photovoltaics, with efficiency records increasing astonishingly fast since their inception. However, problems associated with the stability of these devices are hindering their market application. UV degradation is one of the most severe issues, chiefly caused by TiO2’s photogenerated electrons that decompose the perovskite absorber material, coupled with the additional intrinsic degradation of this material under UV exposure. The solution presented here can minimize this effect while boosting the cells’ generated photocurrent, by making use of combined light-trapping and luminescent down-shifting effects capable of changing the harmful UV radiation to higher wavelengths that do not affect the stability and can be effectively “trapped” in the cell. This work focuses in the optimization of the photocurrent gains that can be attained by emulating the changed spectrum resulting from applying down-shifting media as encapsulant in photonic-enhanced PSCs, as well as the reduction in the harmful effects of UV radiation on the devices. Such optimized photonic solution allows current enhancement while reducing the harmful UV photocarrier generation both in the TiO2 (by 1 order of magnitude) and in the perovskite (by 80%) relative to a standard PSC without light management.

Haque, S, Mendes MJ, Sanchez-Sobrado O, Águas H, Fortunato E, Martins R.  2019.  Photonic-structured TiO2 for high-efficiency, flexible and stable Perovskite solar cells. Nano Energy. 59:91-101. AbstractWebsite

Optical solutions are promising for Perovskite solar cell (PSC) technology, not only to increase efficiency, but also to allow thinner absorber layers (higher flexibility) and improve stability. This work optimized the combined anti-reflection and scattering properties of two types of light trapping (LT) structures, based on TiO2 semi-spheroidal geometries with honeycomb periodicity, for application in PSCs with substrate configuration and different perovskite layer thicknesses. Their optically lossless material (TiO2) allows the structures to be patterned in the final processing steps, integrated in the cells’ top n contact, therefore not increasing the surface area of the PV layers and not degrading the electric performance via recombination. Therefore, this strategy circumvents the typical compromise of state-of-the-art LT approaches between optical improvements and electrical deterioration, which is particularly relevant for PSCs since their main recombination is caused by surface defects. When patterned on the cells’ front, the wave-optical micro-features composing the LT structures yield up to 21% and 27% photocurrent enhancement in PSCs with conventional (500 nm thick) and ultra-thin (250 nm) perovskite layers, respectively; which are improvements close to those predicted by theoretical Lambertian limits. In addition, such features are shown to provide an important encapsulation role, preventing the cells’ degradation from UV penetration.

Berg, AI, Brivio S, Brown S, Burr G, Deswal S, Deuermeier J, Gale E, Hwang H, Ielmini D, Indiveri G, Kenyon AJ, Kiazadeh A, Köymen I, Kozicki M, Li Y, Mannion D, Prodromakis T, Ricciardi C, Siegel S, Speckbacher M, Valov I, Wang W, Williams RS, Wouters D, Yang Y.  2019.  Synaptic and neuromorphic functions: General discussion. Faraday Discussions. 213:553-578. AbstractWebsite
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Aono, M, Baeumer C, Bartlett P, Brivio S, Burr G, Burriel M, Carlos E, Deswal S, Deuermeier J, Dittmann R, Du H, Gale E, Hambsch S, Hilgenkamp H, Ielmini D, Kenyon AJ, Kiazadeh A, Kindsmüller A, Kissling G, Köymen I, Menzel S, Pla Asesio D, Prodromakis T, Santamaria M, Shluger A, Thompson D, Valov I, Wang W, Waser R, Williams RS, Wrana D, Wouters D, Yang Y, Zaffora A.  2019.  Valence change ReRAMs (VCM) - Experiments and modelling: General discussion. Faraday Discussions. 213:259-286. AbstractWebsite
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2018
Das, K, Beyene BB, Datta A, Garribba E, Roma-Rodrigues C, Silva A, Fernandes AR, Hung C-H.  2018.  EPR and electrochemical interpretation of bispyrazolylacetate anchored Ni(ii) and Mn(ii) complexes: cytotoxicity and anti-proliferative activity towards human cancer cell lines, 2018. New Journal of Chemistry. 42(11):9126-9139. AbstractWebsite

Two mononuclear NiII and MnII compounds, [Ni(bdtbpza)2(CH3OH)4] (1) and [Mn(bdtbpza)2(CH3OH)2(H2O)2] (2), are afforded by employing a ‘scorpionate’ type precursor [bdtbpza = bis(3,5-di-t-butylpyrazol-1-yl)acetate]. The single crystal X-ray structure reveals that the central metal ion (NiII for 1 and MnII for 2) is surrounded by a pair of Oacetate atoms of two bis(pyrazol-1-yl)acetate units, while four OMeOH donors for 1 and two OMeOH plus two Owater for 2 complete the first coordination sphere. Thus, both compounds exhibit a slightly distorted octahedral geometry possessing an O6 coordination environment. EPR spectra of CuII-doped 1 and of 2 recorded on the polycrystalline solids and in organic solution confirm the octahedral geometry around the metal ions and the binding of six oxygen atoms. The electrochemical study of compounds 1 and 2 shows that one electron reduction of MnII occurs at a more negative potential than NiII, indicating a lower tendency of reduction for Mn than Ni. Both compounds displayed a high cytotoxic activity against A2780 ovarian carcinoma cells and no cytotoxic activity in normal primary human fibroblasts for concentrations up to 55 μM. Notwithstanding, compound 1 is found to be the most cytotoxic towards A2780 cancer cells. The cytotoxic activity of compound 1 is correlated with the induction of apoptosis associated with a higher mitochondria dysfunction and autophagy cell death. In addition, the compounds can induce oxidative damage leading to ROS accumulation. Overall, the data presented here demonstrate that 1 has potential for further in vivo studies aiming at its future application in ovarian cancer therapy.

Mendes, MJ, Haque S, Sanchez-Sobrado O, Araújo A, Águas H, Fortunato E, Martins R.  2018.  Optimal-Enhanced Solar Cell Ultra-thinning with Broadband Nanophotonic Light Capture, 2018. iScienceiScience. 3:238-254.: Elsevier AbstractWebsite
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Baptista, AC, Ropio I, Romba B, Nobre J, Henriques C, Silva JC, Martins JI, Borges JP, Ferreira I.  2018.  Cellulose-based electrospun fibers functionalized with polypyrrole and polyaniline for fully organic batteries. Journal of Materials Chemistry A. 6(1):256-265. AbstractWebsite

A novel cellulose-based bio-battery made of electrospun fibers activated by biological fluids has been developed. This work reports a new concept for a fully organic bio-battery that takes advantage of the high surface to volume ratio achieved by an electrospun matrix composed of sub-micrometric fibers that acts simultaneously as the separator and the support of the electrodes. Polymer composites of polypyrrole (PPy) and polyaniline (PANI) with cellulose acetate (CA) electrospun matrix were produced by in situ chemical oxidation of pyrrole and aniline on the CA fibers. The structure (CA/PPy|CA|CA/PANI) generated a power density of 1.7 mW g−1 in the presence of simulated biological fluids, which is a new and significant contribution to the domain of medical batteries and fully organic devices for biomedical applications.

Baptista, AC, Ropio I, Romba B, Nobre JP, Henriques C, Silva JC, Martins JI, Borges JP, Ferreira I.  2018.  Cellulose-based electrospun fibers functionalized with polypyrrole and polyaniline for fully organic batteries. J Mater Chem A. 6(1):256-265. AbstractWebsite

A novel cellulose-based bio-battery made of electrospun fibers activated by biological fluids has been developed. This work reports a new concept for a fully organic bio-battery that takes advantage of the high surface to volume ratio achieved by an electrospun matrix composed of sub-micrometric fibers that acts simultaneously as the separator and the support of the electrodes. Polymer composites of polypyrrole (PPy) and polyaniline (PANI) with cellulose acetate (CA) electrospun matrix were produced by in situ chemical oxidation of pyrrole and aniline on the CA fibers. The structure (CA/PPy|CA|CA/PANI) generated a power density of 1.7 mW g−1 in the presence of simulated biological fluids, which is a new and significant contribution to the domain of medical batteries and fully organic devices for biomedical applications.

Ruivo, A, Coutino-Gonzalez E, Santos MM, Baekelant W, Fron E, Roeffaers MBJ, Pina F, Hofkens J, C.A.T. L.  2018.  Highly Photoluminescent Sulfide Clusters Confined in Zeolites. Journal of Physical Chemistry C. 122:14761-14770.
Reckien, D, Heidrich O, Church J, Pietrapertos F, De Gregorio-Hurtado S, D'Alonzo V, Foley A, Simoes SG, Lorencová EK, Orruk H, Orrum K, Wejs A, Flacke J, Olazabal M, Geneletti D, Feliu E, Vasilier S, Nador C, Krook-Riekkola A, Matosović M, A. Fokaides P, I. Ioannou B, Flamos A, Spyridaki N.  2018.  How are cities planning to respond to climate change? Assessment of local climate plans from 885 cities in the EU-28 Journal of Cleaner Production. doi: 10.1016/j.jclepro.2018.03.220. 191:207-219.
Vieira, T, Silva JC, Borges JP, Henriques C.  2018.  Synthesis, electrospinning and in vitro test of a new biodegradable gelatin-based poly(ester urethane urea) for soft tissue engineering. European Polymer Journal. 103:271-281. AbstractWebsite

Biodegradable polyurethanes have been studied as scaffolds for tissue engineering due to their adjustable physico-chemical properties. In this work, we synthesized a biodegradable gelatin-based poly(urethane urea) using polycaprolactone-diol, as soft segment, and isophorone diisocyanate and gelatin from cold water fish skin as hard segment. The synthesis was confirmed by Fourier transform infrared spectroscopy and proton nuclear magnetic resonance and the influence of the amount of gelatin introduced in the polymer backbone was analyzed by thermal analysis. Gelatin-based poly(urethane urea) electrospun fibrous mats and solvent cast films were then produced and their physico-chemical and biological properties studied. They present an amorphous structure, elastomeric behavior and water contact angles typical of hydrophobic surfaces. Hydrolytic degradation was analyzed in phosphate buffer saline (PBS), lipase and trypsin solutions. No mass changes were detected during 37 days in PBS and trypsin while significant degradation by lipase was observed. Human foetal foreskin fibroblasts were seeded on the fibrous mats and films. Populations were evaluated by colorimetric cell viability assays and morphology by fluorescence imaging. The substrates supported cell adhesion and proliferation. The novel gelatin-based poly(urethane urea) fibrous mats offer attractive physico-chemical and biological properties for soft tissue engineering applications.

Larsen, SR, Hansteen M, Pacakova B, Theodor K, Arnold T, Rennie AR, Helgesen G, Knudsen KD, Bordallo HN, Fossum JO, Cavalcanti LP.  2018.  Sample Cell for Studying Liquid Interfaces with an {\emph{in Situ}} Electric Field Using {{X}}-Ray Reflectivity and Application to Clay Particles at Oil–{}Oil Interfaces. Journal of Synchrotron Radiation. 25:915-917., Number 3 Abstract
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2017
Raposo, {LR }, Roma-Rodrigues C, Faísca P, Alves M, Henriques J, Carvalheiro {MC }, Corvo {ML }, Baptista {PV }, Pombeiro {AJ }, Fernandes {AR }.  2017.  Immortalization and characterization of a new canine mammary tumour cell line FR37-CMT, sep. Veterinary and Comparative Oncology. 15:952–967., Number 3: Wiley-Blackwell Abstract

Here we describe the establishment of a new canine mammary tumour (CMT) cell line, FR37-CMT that does not show dependence on female hormonal signaling to induce tumour xenografts in NOD-SCID mice. FR37-CMT cell line has a stellate or fusiform shape, displays the ability to reorganize the collagen matrix, expresses vimentin, CD44 and shows the loss of E-cadherin which is considered a fundamental event in epithelial to mesenchymal transition (EMT). The up-regulation of ZEB1, the detection of phosphorylated ERK1/2 and the downregulation of DICER1 and miR-200c are also in accordance with the mesenchymal characteristics of FR37-CMT cell line. FR37-CMT shows a higher resistance to cisplatin (IC50>50 µM) and to doxorubicin (IC50>5.3 µM) compared with other CMT cell lines. These results support the use of FR37-CMT as a new CMT model that may assist the understanding of the molecular mechanisms underlying EMT, CMT drug resistance, fostering the development of novel therapies targeting CMT.

Kryshtafovych, A, Albrecht R, Baslé A, Bule P, Caputo AT, Carvalho AL, Chao KL, Diskin R, Fidelis K, Fontes CMGA, Fredslund F, Gilbert HJ, Goulding CW, Hartmann MD, Hayes CS, Herzberg O, Hill JC, Joachimiak A, Kohring G-W, Koning RI, {Lo Leggio} L, Mangiagalli M, Michalska K, Moult J, Najmudin S, Nardini M, Nardone V, Ndeh D, Nguyen TH, Pintacuda G, Postel S, van Raaij MJ, Roversi P, Shimon A, Singh AK, Sundberg EJ, Tars K, Zitzmann N, Schwede T.  2017.  Target highlights from the first post-PSI CASP experiment (CASP12, May-August 2016), oct. Proteins: Structure, Function, and Bioinformatics. AbstractWebsite

The functional and biological significance of the selected CASP12 targets are described by the authors of the structures. The crystallographers discuss the most interesting structural features of the target proteins and assess whether these features were correctly reproduced in the predictions submitted to the CASP12 experiment. This article is protected by copyright. All rights reserved.

Pedrosa, P, Heuer-Jungemann A, Kanaras {AG }, Fernandes {AR}, Baptista {PV}.  2017.  Potentiating angiogenesis arrest in vivo via laser irradiation of peptide functionalised gold nanoparticles, nov. Journal of Nanobiotechnology. 15, Number 1: BioMed Central (BMC) Abstract

Background: Anti-angiogenic therapy has great potential for cancer therapy with several FDA approved formulations but there are considerable side effects upon the normal blood vessels that decrease the potential application of such therapeutics. Chicken chorioallantoic membrane (CAM) has been used as a model to study angiogenesis in vivo. Using a CAM model, it had been previously shown that spherical gold nanoparticles functionalised with an anti-angiogenic peptide can humper neo-angiogenesis. Results: Our results show that gold nanoparticles conjugated with an anti-angiogenic peptide can be combined with visible laser irradiation to enhance angiogenesis arrest in vivo. We show that a green laser coupled to gold nanoparticles can achieve high localized temperatures able to precisely cauterize blood vessels. This combined therapy acts via VEGFR pathway inhibition, leading to a fourfold reduction in FLT-1 expression. Conclusions: The proposed phototherapy extends the use of visible lasers in clinics, combining it with chemotherapy to potentiate cancer treatment. This approach allows the reduction of dose of anti-angiogenic peptide, thus reducing possible side effects, while destroying blood vessels supply critical for tumour progression.

Huang, RJ, Avo J, Northey T, Chaning-Pearce E, dos Santos PL, Ward JS, Data P, Etherington MK, Fox MA, Penfold TJ, Berberan-Santos MN, Lima JC, Bryce MR, Dias FB.  2017.  The contributions of molecular vibrations and higher triplet levels to the intersystem crossing mechanism in metal-free organic emitters, 2017. Journal of Materials Chemistry C. 5(25):6269-6280. AbstractWebsite
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Pedrosa, P, Heuer-Jungemann A, Kanaras AG, Fernandes AR, Baptista PV.  2017.  Potentiating angiogenesis arrest in vivo via laser irradiation of peptide functionalised gold nanoparticles, 2017. 15(1):85. AbstractWebsite

Anti-angiogenic therapy has great potential for cancer therapy with several FDA approved formulations but there are considerable side effects upon the normal blood vessels that decrease the potential application of such therapeutics. Chicken chorioallantoic membrane (CAM) has been used as a model to study angiogenesis in vivo. Using a CAM model, it had been previously shown that spherical gold nanoparticles functionalised with an anti-angiogenic peptide can humper neo-angiogenesis.

Simoes, SG, Halstead M, Selosse S, Assoumou E.  2017.  Enhancement of the ETSAP E-Techs Database with water consumption and withdrawal data, 13 December. ETSAP Workshop on modelling the water-energy nexus. , Zurich, Switzerland: ETH Zurich
Maia, LB, Moura I, Moura JJG.  2017.  EPR spectroscopy on mononuclear molybdenum-containing enzymes. Future Directions in Metalloprotein and Metalloenzyme Research, Biological Magnetic Resonance, Vol. 33 (ISBN: 978-3-319-59100-1). (Hanson, G., Berliner, L.J., Eds.).:55-101., Cham: Springer International Publishing Abstract

The biological relevance of molybdenum was demonstrated in the early 1950s-1960s, by Bray, Beinert, Lowe, Massey, Palmer, Ehrenberg, Pettersson, Vänngård, Hanson and others, with ground-breaking studies performed, precisely, by electron paramagnetic resonance (EPR) spectroscopy. Those earlier studies, aimed to investigate the mammalian xanthine oxidase and avian sulfite oxidase enzymes, demonstrated the surprising biological reduction of molybdenum to the paramagnetic Mo5+. Since then, EPR spectroscopy, alongside with other spectroscopic methods and X-ray crystallography, has contributed to our present detailed knowledge about the active site structures, catalytic mechanisms and structure/activity relationships of the molybdenum-containing enzymes.
This Chapter will provide a perspective on the contribution that EPR spectroscopy has made to some selected systems. After a brief overview on molybdoenzymes, the Chapter will be focused on the EPR studies of mammalian xanthine oxidase, with a brief account on the prokaryotic aldehyde oxidoreductase, nicotinate dehydrogenase and carbon monoxide dehydrogenase, vertebrate sulfite oxidase, and prokaryotic formate dehydrogenases and nitrate reductases.

Krings, B-J, Decker M, Weinberger N, Hirsch J.  2017.  Imagined technology futures in demand-oriented technology assessment. Journal of Responsible Innovation. 4(2):177-196.
Loureiro, J, Mateus T, Filonovich S, Ferreira M, Figueira J, Rodrigues A, Donovan BF, Hopkins PE, Ferreira I.  2017.  Improved thermoelectric properties of nanocrystalline hydrogenated silicon thin films by post-deposition thermal annealing. Thin Solid Films. 642:276-280. AbstractWebsite

The influence of post-deposition thermal annealing on the thermoelectric properties of n-and p-type nanocrystalline hydrogenated silicon thin films, deposited by plasma enhanced chemical vapour deposition, was studied in this work. The Power Factor of p-type films was improved from 7× 10− 5 to 4× 10− 4 W/(mK 2) as the annealing temperature, under vacuum, increased up to 400° C while for n-type films it has a minor influence. Optimized Seebeck coefficient values of 460 μV/K and− 320 μV/K were achieved for p-and n-type films, respectively, with crystalline size in the range of 10 nm, leading to remarkable low thermal conductivity values (< 10 Wm− 1. K− 1) at room temperature.

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