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2014
Costa, MN, Veigas B, Jacob JM, Santos DS, Gomes J, Baptista PV, Martins R, Inácio J, Fortunato E.  2014.  {A low cost, safe, disposable, rapid and self-sustainable paper-based platform for diagnostic testing: lab-on-paper.}. Nanotechnology. 25:094006., Number 9 AbstractWebsite

There is a strong interest in the use of biopolymers in the electronic and biomedical industries, mainly towards low-cost applications. The possibility of developing entirely new kinds of products based on cellulose is of current interest, in order to enhance and to add new functionalities to conventional paper-based products. We present our results towards the development of paper-based microfluidics for molecular diagnostic testing. Paper properties were evaluated and compared to nitrocellulose, the most commonly used material in lateral flow and other rapid tests. Focusing on the use of paper as a substrate for microfluidic applications, through an eco-friendly wax-printing technology, we present three main and distinct colorimetric approaches: (i) enzymatic reactions (glucose detection); (ii) immunoassays (antibodies anti-Leishmania detection); (iii) nucleic acid sequence identification (Mycobacterium tuberculosis complex detection). Colorimetric glucose quantification was achieved through enzymatic reactions performed within specific zones of the paper-based device. The colouration achieved increased with growing glucose concentration and was highly homogeneous, covering all the surface of the paper reaction zones in a 3D sensor format. These devices showed a major advantage when compared to the 2D lateral flow glucose sensors, where some carryover of the coloured products usually occurs. The detection of anti-Leishmania antibodies in canine sera was conceptually achieved using a paper-based 96-well enzyme-linked immunosorbent assay format. However, optimization is still needed for this test, regarding the efficiency of the immobilization of antigens on the cellulose fibres. The detection of Mycobacterium tuberculosis nucleic acids integrated with a non-cross-linking gold nanoprobe detection scheme was also achieved in a wax-printed 384-well paper-based microplate, by the hybridization with a species-specific probe. The obtained results with the above-mentioned proof-of-concept sensors are thus promising towards the future development of simple and cost-effective paper-based diagnostic devices.

Branquinho, R, Salgueiro D, Santos L??dia, Barquinha P, Pereira L??s, Martins R, Fortunato E.  2014.  {Aqueous combustion synthesis of aluminum oxide thin films and application as gate dielectric in GZTO solution-based TFTs}. ACS Applied Materials and Interfaces. 6:19592–19599., Number 22 Abstract

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).

Zanarini, S, Garino N, Nair JR, Francia C, Wojcik PJ, Pereira L, Fortunato E, Martins R, Bodoardo S, Penazzi N.  2014.  {Contrast Enhancement in Polymeric Electrochromic Devices Encompassing Room Temperature Ionic Liquids}. International Journal of Electrochemical Science. 9:1650–1662., Number 4 Abstract
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Nunes, D, Pimentel A, Barquinha P, Carvalho PA, Fortunato E, Martins R.  2014.  {Cu2O polyhedral nanowires produced by microwave irradiation}. JOURNAL OF MATERIALS CHEMISTRY C. 2:6097–6103., Number 30 Abstract
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Pereira, S, Gonçalves A, Correia N, Pinto J, Pereira LÍ, Martins R, Fortunato E.  2014.  {Electrochromic behavior of NiO thin films deposited by e-beam evaporation at room temperature}. Solar Energy Materials and Solar Cells. 120, Part:109–115. AbstractWebsite

In this work we report the role of thickness on electrochromic behavior of nickel oxide (NiO) films deposited by e-beam evaporation at room temperature on ITO-coated glass. The structure and morphology of films with thicknesses between 100 and 500 nm were analyzed and then correlated with electrochemical response and transmittance modulation when immersed in 0.5 M LiClO4–PC electrolyte. The NiO exhibits an anodic coloration, reaching for the thickest film a transmittance modulation of 66{%} between colored and bleached state, at 630 nm, with a color efficiency of 55 cm2 C−1. Very fast switch between states was obtained, where coloration and bleaching times are 3.6 s cm−2 and 1.4 s cm−2, respectively.

Zubizarreta, C, Berasategui EG, Bayon R, Galindo ER, Barros R, Gaspar D, Nunes D, Calmeiro T, Martins R, Fortunato E, Barriga J.  2014.  {Evaluation of the optoelectronic properties and corrosion behavior of Al2O3-doped ZnO films prepared by dc pulsed magnetron sputtering}. JOURNAL OF PHYSICS D-APPLIED PHYSICS. 47, Number 48 Abstract
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Bernacka-Wojcik, I, Ribeiro S, Wojcik PJ, Alves PU, Busani T, Fortunato E, Baptista PV, Covas JA, Águas H, Hilliou L, Martins R.  2014.  {Experimental optimization of a passive planar rhombic micromixer with obstacles for effective mixing in a short channel length}. RSC Advances. 4:56013–56025., Number 99 AbstractWebsite

This paper presents the performance of a passive planar rhombic micromixer with diamond-shaped obstacles and a rectangular contraction between the rhombi. The device was experimentally optimized using water for high mixing efficiency and a low pressure drop over a wide range of Reynolds numbers (Re = 0.1–117.6) by varying geometrical parameters such as the number of rhombi, the distance between obstacles and the contraction width. Due to the large amount of data generated, statistical methods were used to facilitate and improve the results of the analysis. The results revealed a rank of factors influencing mixing efficiency: Reynolds number {\textgreater} number of rhombi {\textgreater} contraction width {\textgreater} inter-obstacles distance. The pressure drop measured after three rhombi depends mainly on Re and inter-obstacle distance. The resulting optimum geometry for the low Re regime has a contraction width of 101 $μ$m and inter-obstacles distance of 93 $μ$m, while for the high Re regime a contraction width of 400 $μ$m and inter-obstacle distance of 121 $μ$m are more appropriate. These mixers enabled 80{%} mixing efficiency creating a pressure drop of 6.0 Pa at Re = 0.1 and 5.1 × 104 Pa at Re = 117.6, with a mixer length of 2.5 mm. To the authors' knowledge, the developed mixer is one of the shortest planar passive micromixers reported to date.

Liu, A, Liu GX, Zhu HH, Xu F, Fortunato E, Martins R, Shan FK.  2014.  {Fully Solution-Processed Low-Voltage Aqueous In2O3 Thin-Film Transistors Using an Ultrathin ZrOx Dielectric}. ACS Applied Materials {&} Interfaces. 6:17364–17369., Number 20 AbstractWebsite

We reported here ?aqueous-route? fabrication of In2O3 thin-film transistors (TFTs) using an ultrathin solution-processed ZrOx dielectric thin film. The formation and properties of In2O3 thin films under various annealing temperatures were intensively examined by thermogravimetric analysis, Fourier transform infrared spectroscopy, and atomic force microscopy. The solution-processed ZrOx thin film followed by sequential UV/ozone treatment and low-temperature thermal-annealing processes showed an amorphous structure, a low leakage-current density (?1 ? 10?9 A/cm2 at 2 MV/cm), and a high breakdown electric field (?7.2 MV/cm). On the basis of its implementation as the gate insulator, the In2O3 TFTs based on ZrOx annealed at 250 °C exhibit an on/off current ratio larger than 107, a field-effect mobility of 23.6 cm2/V·s, a subthreshold swing of 90 mV/decade, a threshold voltage of 0.13 V, and high stability. These promising properties were obtained at a low operating voltage of 1.5 V. These results suggest that ?aqueous-route? In2O3 TFTs based on a solution-processed ZrOx dielectric could potentially be used for low-cost, low-temperature-processing, high-performance, and flexible devices.

Liu, GX, Liu A, Shan FK, Meng Y, Shin BC, Fortunato E, Martins R.  2014.  {High-performance fully amorphous bilayer metal-oxide thin film transistors using ultra-thin solution-processed ZrOx dielectric}. Applied Physics Letters. 105:113509., Number 11 AbstractWebsite

In this study, we report high-performance amorphous In2O3/InZnO bilayer metal-oxide (BMO) thin-film transistor (TFT) using an ultra-thin solution-processed amorphous ZrOx dielectric. A thin layer of In2O3 offers a higher carrier concentration, thereby maximizing the charge accumulation and yielding high carrier mobility. A thick amorphous layer of InZnO controls the charge conductance resulting in low off-state current and suitable threshold voltage. As a consequence, the BMO TFT showed higher filed-effect mobility (37.9 cm2/V s) than single-layer InZnO TFT (7.6 cm2/V s). Apart from that we obtain an on/off current ratio of 109, a subthreshold swing voltage of 120 mV/decade, and a voltage shift ≤ 0.4 V under positive bias stress for 2.5 h, for a gate voltage of 3 V and drain voltage of 1 V. These data demonstrate that the BMO TFT has great potential for a broad range of applications as switching low-power transistors.

Araujo, A, Caro C, Mendes MJ, Nunes D, Fortunato E, Franco R, Aguas H, Martins R.  2014.  {Highly efficient nanoplasmonic SERS on cardboard packaging substrates}. NANOTECHNOLOGY. 25, Number 41 Abstract
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Veigas, B, Branquinho R, Pinto JV, Wojcik PJ, Martins R, Fortunato E, Baptista PV.  2014.  {Ion sensing (EIS) real-time quantitative monitorization of isothermal DNA amplification}. Biosensors and Bioelectronics. 52:50–55. AbstractWebsite

Field-effect-based devices are becoming a basic structural element in a new generation of microbiosensors. Reliable molecular characterization of DNA and/or RNA is of paramount importance for disease diagnostics and to follow up alterations in gene expression profiles. The use of such devices for point-of-need diagnostics has been hindered by the need of standard or real-time PCR amplification procedures. The present work focuses on the development of a tantalum pentoxide (Ta2O5) based sensor for the real-time label free detection of DNA amplification via loop mediated isothermal amplification (LAMP) allowing for quantitative analysis of the cMYC proto-oncogene. The strategy based on the field effect sensor was tested within a range of 1×108–1011 copies of target DNA, and a linear relationship between the log copy number of the initial template DNA and threshold time was observed allowing for a semi-quantitative analysis of DNA template. The concept offers many of the advantages of isothermal quantitative real-time DNA amplification in a label free approach and may pave the way to point-of-care quantitative molecular analysis focused on ease of use and low cost.

Gaspar, D, Fernandes SN, de Oliveira AG, Fernandes JG, Grey P, Pontes RV, Pereira L, Martins R, Godinho MH, Fortunato E.  2014.  {Nanocrystalline cellulose applied simultaneously as the gate dielectric and the substrate in flexible field effect transistors}. Nanotechnology. 25:94008., Number 9 AbstractWebsite

Cotton-based nanocrystalline cellulose (NCC), also known as nanopaper, one of the major sources of renewable materials, is a promising substrate and component for producing low cost fully recyclable flexible paper electronic devices and systems due to its properties (lightweight, stiffness, non-toxicity, transparency, low thermal expansion, gas impermeability and improved mechanical properties). Here, we have demonstrated for the first time a thin transparent nanopaper-based field effect transistor (FET) where NCC is simultaneously used as the substrate and as the gate dielectric layer in an ‘interstrate' structure, since the device is built on both sides of the NCC films; while the active channel layer is based on oxide amorphous semiconductors, the gate electrode is based on a transparent conductive oxide. Such hybrid FETs present excellent operating characteristics such as high channel saturation mobility ({\textgreater}7 cm 2 V −1 s −1 ), drain–source current on/off modulation ratio higher than 10 5 , enhancement n-type operation and subthreshold gate voltage swing of 2.11 V/decade. The NCC film FET characteristics have been measured in air ambient conditions and present good stability, after two weeks of being processed, without any type of encapsulation or passivation layer. The results obtained are comparable to ones produced for conventional cellulose paper, marking this out as a promising approach for attaining high-performance disposable electronics such as paper displays, smart labels, smart packaging, RFID (radio-frequency identification) and point-of-care systems for self-analysis in bioscience applications, among others.

Pimentel, A, Nunes D, Duarte P, Rodrigues J, Costa FM, Monteiro T, Martins R, Fortunato E.  2014.  {Synthesis of Long ZnO Nanorods under Microwave Irradiation or Conventional Heating}. The Journal of Physical Chemistry C. 118:14629–14639., Number 26 AbstractWebsite

The present work reports the synthesis of zinc oxide (ZnO) nanostructures produced either under microwave irradiation using low cost domestic microwave equipment or by conventional heating, both under hydrothermal conditions. X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, room/low temperature photoluminescence, and Raman spectroscopy have been used to investigate the structure, morphology, and optical properties of the produced ZnO nanorods. Identical structures with aspect ratio up to 13 have been achieved for both synthesis routes displaying similar final properties. The hexagonal wurtzite structure has been identified, and a red-orange emission has been detected in the presence of UV irradiation for all the conditions studied. Thermal stability of the as-prepared nanostructures has been evaluated through thermogravimetric measurements revealing an increase of superficial defects. The as-prepared ZnO nanorods were tested as UV sensors on paper substrate, which led to fast response (30 s) and rapid recovery (100 s) times, as well as sensitivity up to 10 indicating that these materials may have a high potential in low cost, disposable UV photodetector applications.

Pereira, L, Gaspar D, Guerin D, a Delattre, Fortunato E, Martins R.  2014.  {The influence of fibril composition and dimension on the performance of paper gated oxide transistors}. Nanotechnology. 25:94007., Number 9 AbstractWebsite

Paper electronics is a topic of great interest due the possibility of having low-cost, disposable and recyclable electronic devices. The final goal is to make paper itself an active part of such devices. In this work we present new approaches in the selection of tailored paper, aiming to use it simultaneously as substrate and dielectric in oxide based paper field effect transistors (FETs). From the work performed, it was observed that the gate leakage current in paper FETs can be reduced using a dense microfiber/nanofiber cellulose paper as the dielectric. Also, the stability of these devices against changes in relative humidity is improved. On other hand, if the pH of the microfiber/nanofiber cellulose pulp is modified by the addition of HCl, the saturation mobility of the devices increases up to 16 cm 2 V −1 s −1 , with an I ON / I OFF ratio close to 10 5 .

Santos, L, Neto JP, Crespo A, Nunes D, Costa N, Fonseca IM, Barquinha P, Pereira LÍ, Silva J, Martins R, Fortunato E.  2014.  {WO3 Nanoparticle-Based Conformable pH Sensor}. ACS Applied Materials {&} Interfaces. 6:12226–12234., Number 15 AbstractWebsite

pH is a vital physiological parameter that can be used for disease diagnosis and treatment as well as in monitoring other biological processes. Metal/metal oxide based pH sensors have several advantages regarding their reliability, miniaturization, and cost-effectiveness, which are critical characteristics for in vivo applications. In this work, WO3 nanoparticles were electrodeposited on flexible substrates over metal electrodes with a sensing area of 1 mm2. These sensors show a sensitivity of ?56.7 ± 1.3 mV/pH, in a wide pH range of 9 to 5. A proof of concept is also demonstrated using a flexible reference electrode in solid electrolyte with a curved surface. A good balance between the performance parameters (sensitivity), the production costs, and simplicity of the sensors was accomplished, as required for wearable biomedical devices.

2013
Amaro, P, Schlesser S, Guerra M, Le Bigot E, Santos JP, Szabo CI, Gumberidze A, Indelicato P.  2013.  Absolute measurements and simulations of x-ray line energies of highly charged ions with a double-crystal spectrometer, Sep 23. Physica Scripta. T156:014104. AbstractWebsite
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Szabo, CI, Amaro P, Guerra M, Santos JP, Gumberidze A, Attard J, Indelicato P.  2013.  Ion temperature and x-ray line width measurements of highly charged argon ions in an ECR ion source, Sep 23. Physica Scripta. T156:014077. AbstractWebsite
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Santos, JP, Marques JP, Costa AM, Martins MC, Indelicato P, Parente F.  2013.  Transition probability values of the 1s 22s3p 3P 0level in Be-like ions, Sep 23. Physica Scripta. T156:014020. AbstractWebsite
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Branquinho, R, {Vaz Pinto} J, Busani {TL}, Barquinha {PMC}, Pereira {LMN}, Baptista {PMRV}, de Martins {RFP}, Fortunato {EMC}.  2013.  Plastic Compatible Sputtered Ta2O5 Sensitive Layer for Oxide Semiconductor TFT Sensors, sep. Journal Of Display Technology. 9:723–728., Number 9: IEEE Computer Society Abstract

The effect of post-deposition annealing temperature on the pH sensitivity of room temperature RF sputtered Ta2O5 was investigated. Structural and morphological features of these films were analyzed before and after annealing at various temperatures. The deposited films are amorphous up to 600 degrees C and crystallize at 700 degrees C in an orthorhombic phase. Electrolyte-insulator-semiconductor (EIS) field effect based sensors with an amorphous Ta2O5 sensing layer showed pH sensitivity above 50 mV/pH. For sensors annealed above 200 degrees C pH sensitivity decreased with increasing temperature. Stabilized sensor response and maximum pH sensitivity was achieved after low temperature annealing at 200 degrees C, which is compatible with the use of polymeric substrates and application as sensitive layer in oxides TFT-based sensors.

Sousa, DG, Ferreira C, Lourenço JM.  2013.  Prevenção de Violações de Atomicidade usando Contractos, sep. Proceedings of INForum Simpósio de Informática. :190–201., Lisbon, Portugal: Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa Abstract2013-inforum-ds.pdf

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Martins, HRL, Soares J, Lourenço JM, Preguiça N.  2013.  Replicação Multi-nível de Bases de Dados em Memória, sep. Proceedings of INForum Simpósio de Informática. :190–201., Lisbon, Portugal: Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa Abstract2013-inforum-hm.pdf

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Bernacka-Wójcik, I, Lopes {PA }, Vaz {AC}, Veigas {BMR}, Wojcik {PJ}, Simões P, Barata D, Fortunato {EMC}, Baptista {PMRV}, Águas {HMB}, de Martins {RFP}.  2013.  Bio-microfluidic platform for gold nanoprobe based DNA detection-application to Mycobacterium tuberculosis, oct. Biosensors & Bioelectronics. 48:87–93.: Elsevier Abstract

We have projected and fabricated a microfluidic platform for DNA sensing that makes use of an optical colorimetric detection method based on gold nanoparticles. The platform was fabricated using replica moulding technology in PDMS patterned by high-aspect-ratio SU-8 moulds. Biochips of various geometries were tested and evaluated in order to find out the most efficient architecture, and the rational for design, microfabrication and detection performance is presented. The best biochip configuration has been successfully applied to the DNA detection of Mycobacterium tuberculosis using only 3 mu l on DNA solution (i.e. 90 ng of target DNA), therefore a 20-fold reduction of reagents volume is obtained when compared with the actual state of the art.

Cordeiro, M, Giestas L, Lima {JC }, Baptista P.  2013.  Coupling an universal primer to SBE combined spectral codification strategy for single nucleotide polymorphism analysis, oct. Journal of Biotechnology. 168:90–94., Number 1: Elsevier Abstract

We previously reported a strategy that combines Forster resonance energy transfer (FRET) based spectral codification with a single base extension (SBE) reaction for single nucleotide sequence discrimination in solution. This strategy is capable of unequivocally detect the allele variants present in solution. To extend the use of this tool to any locus of interest, it would be required the development of an universal approach capable of combining a sequence specific SBE primer to an universal sequence labeled and optimized for spectral codification.Here, we extend this concept to a general strategy by means of a labeled universal oligonucleotide primer (donor), a sequence specific primer that allows for incorporation of the complementary acceptor labeled ddNTP, which allows discrimination the allele variant in the sample via the unambiguous FRET signature of the donor/acceptor pair

Conde, J, Tian F, Hernández Y, Bao C, Cui D, Janssen {KP}, Ibarra R}{M, Baptista {PV}, Stoeger T, {de la Fuente} {JM }.  2013.  Invivo tumor targeting via nanoparticle-mediated therapeutic siRNA coupled to inflammatory response in lung cancer mouse models, oct. Biomaterials. 34:7744–7753., Number 31: Elsevier Abstract

Up to now, functionalized gold nanoparticles have been optimized as an effective intracellular invitro delivery vehicle for siRNAs to interfere with the expression of specific genes by selective targeting, and provide protection against nucleases. Few examples however of suchlike invivo applications have been described so far. In this study, we report the use of siRNA/RGD gold nanoparticles capable of targeting tumor cells in a lung cancer syngeneic orthotopic murine model. Therapeutic RGD-nanoparticle treatment resulted in successful targeting evident from significant c-myc oncogene down-regulation followed by tumor growth inhibition and prolonged survival of lung tumor bearing mice, possibly via αvβ3 integrin interaction. Our results suggest that RGD gold nanoparticles-mediated delivery of siRNA by intratracheal instillation in mice leads to successful suppression of tumor cell proliferation and respective tumor size reduction. These results reiterate the capability of functionalized gold nanoparticles for targeted delivery of siRNA to cancer cells towards effective silencing of the specific target oncogene. What is more, we demonstrate that the gold-nanoconjugates trigger a complex inflammatory and immune response that might promote the therapeutic effect of the RNAi to reduce tumor size with low doses of siRNA.