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2015
Baptista, A. C., A. M. Botas, A. P. C. Almeida, A. T. Nicolau, B. P. Falcão, M. J. Soares, J. P. Leitão, R. Martins, J. P. Borges, and I. Ferreira, "Down conversion photoluminescence on PVP/Ag-nanoparticles electrospun composite fibers", Opt. Mater., vol. 39, pp. 278-281, 2015. AbstractDOI

The influence of Ag nanoparticles (Ag NPs) on the luminescence of electrospun nonwoven mats made of polyvinylpyrrolidone (PVP) has been studied in this work. The PVP fibers incorporating 2.1–4.3 nm size Ag NPs show a significant photoluminescence (PL) band between 580 and 640 nm under 325 nm laser excitation. The down conversion luminescence emission is present even after several hours of laser excitation, which denotes the durability and stability of fibers to consecutive excitations. As so these one-dimensional photonic fibers made using cheap methods is of great importance for organic optoelectronic applications, fluorescent clothing or counterfeiting labels.

Muelle, H., P. Barquinha, I. Ferreira, E. Fortunato, M. C. Santos, and M. S. Diniz, "Effects of ultra-sonication on the cyanobacteria Microcystis aeruginosa structure and growth", Microsc. Microanal., vol. 21, pp. 50-51, 2015. AbstractDOI

The eutrophication of surface waters caused by cyanobacteria is a worldwide problem, leading to expensive
water treatment costs [1]. In addition, the production of microcystins by these microalgae may cause many
health problems to humans and animals (e.g. liver cancer) and even death [2]. Therefore, a variety of
methods have been developed to control cyanobacteria blooms, including physical and chemical treatments.
However, they have negative impacts on other species of (micro) algae and on other aquatic biota. As a
consequence, ultrasonic algae treatment has been proposed as a clean approach to controlling the blooms of
some algae species and microcystins degradation [3]. Still, the specific effects of ultra-sonication on
cyanobacteria are not well known. The present work aimed to study the effects of ultra-sonication on the
cyanobacteria structure under different ultrasound conditions (changing frequency and power) by using
conventional histology and electron microscopy methods.
Microcystis spp. were harvested in a lake from Azores (Portugal) and stored in the cool and dark until
transported to the laboratory. Cyanobacteria were cultured in liquid BG-11 axenic medium at 22ºC in an
incubator chamber, under continuous illumination (fluorescent cold white light).
Samples were collected and suspensions of cells (1ml each) were subjected to ultrasonic irradiation using
diverse ultrasonic equipment (UP100H; UP200S, sonoreactor UTR 200 and ultrasonic bath) and testing
different exposure times. All the experimental algal suspensions were exposed for 5 min to ultrasonication
(on ice for periods of 10s to avoid heating). After ultrasonication cyanobacteria growth was assessed for a
period of 14 days and structural changes in cells were evaluated by light (LM) and scanning electron
microscopy (SEM) examination. The results show growth inhibition of the cyanobacteria according to
intensity and power used in each ultrasonic device. The use of the most powerful devices (sonoreactor and
UP200S) resulted in a massive disrupting of cell walls with consequent cell death (Fig. 1e,f). Similar results
were obtained by Ahan et al. [1] and Nakano et al. [4] and showing cell wall disruption. However, even
after exposure to the most powerful instrumentation it was possible to detect some viable cells and after 14
days colonies were already visible. The results from light and electron microscopy showed noticeable
changes at the structural level such as disruption of cell gas vacuoles (arrowhead), colony disaggregation and
damage of cell walls of cells (Fig. 1c-f).
As a consequence, the use of ultrasounds to improve water quality from eutrophic waters must be considered
with careful in terms of efficiency and other complementary methods should be considered to assure good
water quality criteria. In addition, the effects of ultrasonication in other aquatic organisms require further
studies before using this technology to control algae blooms.

Loureiro, J., T. Mateus, S. Filonovich, M. Ferreira, J. Figueira, A. Rodrigues, B. F. Donovan, P. E. Hopkins, and I. Ferreira, "Hydrogenated nanocrystalline silicon thin films with promising thermoelectric properties", Appl. Phys. A, vol. 120, issue 4, pp. 1497–1502, 2015. AbstractDOI

The search for materials with suitable thermoelectric properties that are environmentally friendly and abundant led us to investigate p- and n-type hydrogenated nanocrystalline silicon (nc-Si:H) thin films, produced by plasma-enhanced chemical vapor deposition. The Seebeck coefficient and power factor were measured at room temperature showing optimized values of 512 µV K−1 and 3.6 × 10−5 W m−1 K−2, for p-type, and −188 µV K−1 and 2.2 × 10−4 W m−1 K−2, for n-type thin films. The thermoelectric output power of one nc-Si:H pair of both n- and p-type materials is ~91 µW per material cm3, for a thermal gradient of 8 K. The output voltage and current values show a linear dependence with the number of pairs interconnected in series and/or parallel and show good integration performance.

Picado, A., S. M. Paixão, L. Moita, L. Silva, M. S. Diniz, J. Lourenço, I. Peres, L. Castro, J. B. Correia, J. Pereira, I. Ferreira, A. P. A. Matos, P. Barquinha, and E. Mendonça, "A multi-integrated approach on toxicity effects of engineered TiO2 nanoparticles", Front. Env. Sci. Eng., vol. 9, issue 5, pp. 793–803, 2015. AbstractDOI

The new properties of engineered nanoparticles drive the need for new knowledge on the safety, fate, behavior and biologic effects of these particles on organisms and ecosystems. Titanium dioxide nanoparticles have been used extensively for a wide range of applications, e.g, self-cleaning surface coatings, solar cells, water treatment agents, topical sunscreens. Within this scenario increased environmental exposure can be expected but data on the ecotoxicological evaluation of nanoparticles are still scarce. The main purpose of this work was the evaluation of effects of TiO2 nanoparticles in several organisms, covering different trophic levels, using a battery of aquatic assays. Using fish as a vertebrate model organism tissue histological and ultrastructural observations and the stress enzyme activity were also studied. TiO2 nanoparticles (Aeroxide® P25), two phase composition of anatase (65%) and rutile (35%) with an average particle size value of 27.6±11 nm were used. Results on the EC50 for the tested aquatic organisms showed toxicity for the bacteria, the algae and the crustacean, being the algae the most sensitive tested organism. The aquatic plant Lemna minor showed no effect on growth. The fish Carassius auratus showed no effect on a 21 day survival test, though at a biochemical level the cytosolic Glutathione-S-Transferase total activity, in intestines, showed a general significant decrease (p<0.05) after 14 days of exposure for all tested concentrations. The presence of TiO2 nanoparticles aggregates were observed in the intestine lumen but their internalization by intestine cells could not be confirmed.

Echeverria, C., P. Soares, A. Robalo, L. Pereira, C. M. M. Novo, I. Ferreira, and J. P. Borges, "One-pot synthesis of dual-stimuli responsive hybrid PNIPAAm-chitosan microgels", Mater. Des, vol. 86, pp. 745-751, 2015. AbstractDOI

The incorporation of magnetic nanoparticles into poly(N-isopropylacrylamide) (PNIPAAm) and chitosan microgels gives rise to hybrid systems that combine the microgels swelling capacity with the interesting features presented in magnetic nanoparticles. The presence of chitosan that act as surfactant for magnetic nanoparticles provides a simplistic approach which allows the encapsulation of magnetic nanoparticles without any previous surface modification. Spherical and highly monodisperse microgels with diameters in the range of 200 to 500 nm were obtained. The encapsulation of magnetic nanoparticles in the polymer matrix was confirmed by high resolution Scanning Electron Microscopy in transmission mode. Volume phase transition of the microgels was accessed by Dynamic Light Scattering measurements. It was observed that the thermosensitivity of the PNIPAM microgels still persists in the hybrid microgels; however, the swelling ability is compromised in the microgels with highest chitosan content. The heating performance of the hybrid magnetic microgels, when submitted to an alternating magnetic field, was also evaluated demonstrating the potential of these systems for hyperthermia treatments.

Contreras, J., J. Tornero, I. Ferreira, R. Martins, L. Gomes, and E. Fortunato, "Simulated and Real Sheet-of-Light 3D Object Scanning Using a-Si:H Thin Film PSD Arrays", Sensors, vol. 15, issue 12, pp. 29938-29949, 2015. Abstract

A MATLAB/SIMULINK software simulation model (structure and component blocks) has been constructed in order to view and analyze the potential of the PSD (Position Sensitive Detector) array concept technology before it is further expanded or developed. This simulation allows changing most of its parameters, such as the number of elements in the PSD array, the direction of vision, the viewing/scanning angle, the object rotation, translation, sample/scan/simulation time, etc. In addition, results show for the first time the possibility of scanning an object in 3D when using an a-Si:H thin film 128 PSD array sensor and hardware/software system. Moreover, this sensor technology is able to perform these scans and render 3D objects at high speeds and high resolutions when using a sheet-of-light laser within a triangulation platform. As shown by the simulation, a substantial enhancement in 3D object profile image quality and realism can be achieved by increasing the number of elements of the PSD array sensor as well as by achieving an optimal position response from the sensor since clearly the definition of the 3D object profile depends on the correct and accurate position response of each detector as well as on the size of the PSD array.

Ferreira, M., J. Loureiro, A. Nogueira, A. Rodrigues, R. Martins, and I. Ferreira, "SnO2 thin Film Oxides Produced by rf Sputtering for Transparent Thermoelectric Devices", Mater. Today-Proc, vol. 2, issue 2, pp. 647-653, 2015. AbstractDOI

The combination of high transparency and good thermoelectric properties of SnO2 can open new field of applications for the thin film thermoelectric materials. Here we report on SnO2 thin films with transmittance above 90%, resistivity bellow 10-3 Ωm and a Power Factor around 10-4 W/m.K2, for a Seebeck of -255 μV/K, at room temperature. The effect of film thickness and post-deposition annealing on the thermoelectric properties were analysed. The performances of a single layer thermoelectric device are also presented.

Soares, P. I. P., F. Lochte, C. Echeverria, L. C. J. Pereira, J. T. Coutinho, I. M. M. Ferreira, C. M. M. Novo, and J. P. M. R. Borges, "Thermal and magnetic properties of iron oxide colloids: influence of surfactants", Nanotechnology, vol. 26, issue 42, pp. 425704, 2015. AbstractDOI

Iron oxide nanoparticles (NPs) have been extensively studied in the last few decades for several biomedical applications such as magnetic resonance imaging, magnetic drug delivery and hyperthermia. Hyperthermia is a technique used for cancer treatment which consists in inducing a temperature of about 41–45 °C in cancerous cells through magnetic NPs and an external magnetic field. Chemical precipitation was used to produce iron oxide NPs 9 nm in size coated with oleic acid and trisodium citrate. The influence of both stabilizers on the heating ability and in vitro cytotoxicity of the produced iron oxide NPs was assessed. Physicochemical characterization of the samples confirmed that the used surfactants do not change the particles' average size and that the presence of the surfactants has a strong effect on both the magnetic properties and the heating ability. The heating ability of Fe3O4 NPs shows a proportional increase with the increase of iron concentration, although when coated with trisodium citrate or oleic acid the heating ability decreases. Cytotoxicity assays demonstrated that both pristine and trisodium citrate Fe3O4 samples do not reduce cell viability. However, oleic acid Fe3O4 strongly reduces cell viability, more drastically in the SaOs-2 cell line. The produced iron oxide NPs are suitable for cancer hyperthermia treatment and the use of a surfactant brings great advantages concerning the dispersion of NPs, also allowing better control of the hyperthermia temperature.

2016
Soares, P. I. P., A. I. Sousa, J. C. Silva, I. M. M. Ferreira, C. M. M. Novo, and J. P. Borges, "Chitosan-based nanoparticles as drug delivery systems for doxorubicin: Optimization and modelling", Carbohydr Polym, vol. 147, pp. 304-312, 2016. AbstractDOI

In the present work, two drug delivery systems were produced by encapsulating doxorubicin into chitosan and O-HTCC (ammonium-quaternary derivative of chitosan) nanoparticles. The results show that doxorubicin release is independent of the molecular weight and is higher at acidic pH (4.5) than at physiological pH. NPs with an average hydrodynamic diameter bellow 200 nm are able to encapsulate up to 70% and 50% of doxorubicin in the case of chitosan and O-HTCC nanoparticles, respectively. O-HTCC nanoparticles led to a higher amount of doxorubicin released than chitosan nanoparticles, for the same experimental conditions, although the release mechanism was not altered. A burst effect occurs within the first hours of release, reaching a plateau after 24 h. Fitting mathematical models to the experimental data led to a concordant release mechanism between most samples, indicating an anomalous or mixed release, which is in agreement with the swelling behavior of chitosan described in the literature.

Mendes, M. J., A. Araújo, A. Vicente, H. Águas, I. Ferreira, E. Fortunato, and R. Martins, "Design of optimized wave-optical spheroidal nanostructures for photonic-enhanced solar cells", Nano Energy, vol. 26, pp. 286-296, 2016. AbstractDOI

The interaction of light with wavelength-sized photonic nanostructures is highly promising for light management applied to thin-film photovoltaics. Several light trapping effects come into play in the wave optics regime of such structures that crucially depend on the parameters of the photonic and absorbing elements. Thus, multi-parameter optimizations employing exact numerical models, as performed in this work, are essential to determine the maximum photocurrent enhancement that can be produced in solar cells.

Generalized spheroidal geometries and high-index dielectric materials are considered here to model the design of the optical elements providing broadband absorption enhancement in planar silicon solar cells. The physical mechanisms responsible for such enhancement are schematized in a spectral diagram, providing a deeper understanding of the advantageous characteristics of the optimized geometries. The best structures, composed of TiO2 half-spheroids patterned on the cells' top surface, yield two times higher photocurrent (up to 32.5 mA/cm2 in 1.5 µm thick silicon layer) than the same devices without photonic schemes.

These results set the state-of-the-art closer to the theoretical Lambertian limit. In addition, the considered light trapping designs are not affected by the traditional compromise between absorption enhancement versus current degradation by recombination, which is a key technological advantage.