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2016
Soares, P. I. P., D. Machado, C. Laia, L. C. J. Pereira, J. T. Coutinho, I. M. M. Ferreira, C. M. M. Novo, and J. P. Borges, "Thermal and magnetic properties of chitosan-iron oxide nanoparticles", Carbohydr Polym, vol. 149, pp. 382-390, 2016. AbstractDOI

Chitosan is a biopolymer widely used for biomedical applications such as drug delivery systems, wound healing, and tissue engineering. Chitosan can be used as coating for other types of materials such as iron oxide nanoparticles, improving its biocompatibility while extending its range of applications.

In this work iron oxide nanoparticles (Fe3O4 NPs) produced by chemical precipitation and thermal decomposition and coated with chitosan with different molecular weights were studied. Basic characterization on bare and chitosan-Fe3O4 NPs was performed demonstrating that chitosan does not affect the crystallinity, chemical composition, and superparamagnetic properties of the Fe3O4 NPs, and also the incorporation of Fe3O4 NPs into chitosan nanoparticles increases the later hydrodynamic diameter without compromising its physical and chemical properties. The nano-composite was tested for magnetic hyperthermia by applying an alternating current magnetic field to the samples demonstrating that the heating ability of the Fe3O4 NPs was not significantly affected by chitosan.

2015
Mendes, M. J., S. Morawiec, T. Mateus, A. Lyubchyk, H. Águas, I. Ferreira, E. Fortunato, R. Martins, F. Priolo, and I. Crupi, "Broadband light trapping in thin film solar cells with self-organized plasmonic nano-colloids", Nanotechnology, vol. 26, issue 13, pp. 135202, 2015. AbstractDOI

The intense light scattered from metal nanoparticles sustaining surface plasmons makes them attractive for light trapping in photovoltaic applications. However, a strong resonant response from nanoparticle ensembles can only be obtained if the particles have monodisperse physical properties. Presently, the chemical synthesis of colloidal nanoparticles is the method that produces the highest monodispersion in geometry and material quality, with the added benefits of being low-temperature, low-cost, easily scalable and of allowing control of the surface coverage of the deposited particles. In this paper, novel plasmonic back-reflector structures were developed using spherical gold colloids with appropriate dimensions for pronounced far-field scattering. The plasmonic back reflectors are incorporated in the rear contact of thin film n-i-p nanocrystalline silicon solar cells to boost their photocurrent generation via optical path length enhancement inside the silicon layer. The quantum efficiency spectra of the devices revealed a remarkable broadband enhancement, resulting from both light scattering from the metal nanoparticles and improved light incoupling caused by the hemispherical corrugations at the cells' front surface formed from the deposition of material over the spherically shaped colloids.

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.

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.

2014
Morawiec, S., M. J. Mendes, S. A. Filonovich, T. Mateus, S. Mirabella, H. Águas, I. Ferreira, F. Simone, E. Fortunato, R. Martins, F. Priolo, and I. Crupi, "Photocurrent enhancement in thin a-Si: H solar cells via plasmonic light trapping", CLEO: Science and Innovations: Optical Society of America, 8-13 Jun, 2014. Abstract

Photocurrent enhancement in thin a-Si:H solar cells due to the plasmonic light trapping is investigated, and correlated with the morphology and the optical properties of the self-assembled silver nanoparticles incorporated in the cells’ back reflector.

Gaspar, D., A. C. Pimentel, M. J. Mendes, T. Mateus, B. P. Falcão, J. P. Leitão, J. Soares, A. Araújo, A. Vicente, S. A. Filonovich, H. Águas, R. Martins, and I. Ferreira, "Ag and Sn Nanoparticles to Enhance the Near-Infrared Absorbance of a-Si:H Thin Films", Plasmonics, vol. 9, issue 5, pp. 1015–1023, 2014. AbstractDOI

Silver (Ag) and tin (Sn) nanoparticles (NPs) were deposited by thermal evaporation onto heated glass substrates with a good control of size, shape and surface coverage. This process has the advantage of allowing the fabrication of thin-film solar cells with incorporated NPs without vacuum break, since it does not require chemical processes or post-deposition annealing. The X-ray diffraction, TEM and SEM properties are correlated with optical measurements and amorphous silicon hydrogenated (a-Si:H) films deposited on top of both types of NPs show enhanced absorbance in the near-infrared. The results are interpreted with electromagnetic modelling performed with Mie theory. A broad emission in the near-infrared region is considerably increased after covering the Ag nanoparticles with an a-Si:H layer. Such effect may be of interest for possible down-conversion mechanisms in novel photovoltaic devices.

Morawiec, S., M. J. Mendes, S. A. Filonovich, T. Mateus, S. Mirabella, H. Águas, I. Ferreira, F. Simone, E. Fortunato, R. Martins, F. Priolo, and I. Crupi, "Broadband photocurrent enhancement in a-Si:H solar cells with plasmonic back reflectors", Opt. Express, vol. 22, issue 104, pp. A1059-A1070, 2014. AbstractDOI

Plasmonic light trapping in thin film silicon solar cells is a promising route to achieve high efficiency with reduced volumes of semiconductor material. In this paper, we study the enhancement in the opto-electronic performance of thin a-Si:H solar cells due to the light scattering effects of plasmonic back reflectors (PBRs), composed of self-assembled silver nanoparticles (NPs), incorporated on the cells’ rear contact. The optical properties of the PBRs are investigated according to the morphology of the NPs, which can be tuned by the fabrication parameters. By analyzing sets of solar cells built on distinct PBRs we show that the photocurrent enhancement achieved in the a-Si:H light trapping window (600 – 800 nm) stays in linear relation with the PBRs diffuse reflection. The best-performing PBRs allow a pronounced broadband photocurrent enhancement in the cells which is attributed not only to the plasmon-assisted light scattering from the NPs but also to the front surface texture originated from the conformal growth of the cell material over the particles. As a result, remarkably high values of Jsc and Voc are achieved in comparison to those previously reported in the literature for the same type of devices.

Soares, P. I. P., A. M. R. Alves, L. C. J. Pereira, J. T. Coutinho, I. M. M. Ferreira, C. M. M. Novo, and J. P. M. R. Borges, "Effects of surfactants on the magnetic properties of iron oxide colloids", J. Colloid Interface Sci., vol. 419, pp. 46-51, 2014. AbstractDOI

Iron oxide nanoparticles are having been extensively investigated for several biomedical applications such as hyperthermia and magnetic resonance imaging. However, one of the biggest problems of these nanoparticles is their aggregation.

Taking this into account, in this study the influence of three different surfactants (oleic acid, sodium citrate and Triton X-100) each one with various concentrations in the colloidal solutions stability was analyzed by using a rapid and facile method, the variation in the optical absorbance along time.

The synthesized nanoparticles through chemical precipitation showed an average size of 9 nm and a narrow size distribution. X-ray diffraction pattern and Fourier Transform Infrared analysis confirmed the presence of pure magnetite. SQUID measurements showed superparamagnetic properties with a blocking temperature around 155 K. In addition it was observed that neither sodium citrate nor Triton X-100 influences the magnetic properties of the nanoparticles. On the other hand, oleic acid in a concentration of 64 mM decreases the saturation magnetization from 67 to 45 emu/g. Oleic acid exhibits a good performance as stabilizer of the iron oxide nanoparticles in an aqueous solution for 24 h, for concentrations that lead to the formation of the double layer.