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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.

João, C. F. C., A. C. Baptista, I. M. M. Ferreira, J. C. Silva, and J. P. Borges, "https://vtt.pure.elsevier.com/en/publications/transflexteg-large-area-transparent-thin-film-thermoelectric-devi", Fibrous and textile materials for composite applications, Singapore, Springer, pp. 261-299, 2016. Abstract

Cellulose and chitin are the two most abundant natural polysaccharides. Both have a semicrystalline microfibrillar structure from which nanofibres can be extracted. These nanofibres are rod-like microcrystals that can be used as nanoscale reinforcements in composites due to their outstanding mechanical properties. This chapter starts by reviewing the sources, extraction methods and properties of cellulose and chitin nanofibres. Then, their use in the fabrication of structural and functional nanocomposites and the applications that have been investigated are reviewed. Nanocomposites are materials with internal nano-sized structures. They benefit from the properties of the nanofillers: low density, nonabrasive, nontoxic, low cost, susceptibility to chemical modifications and biodegradability. Diverse manufacturing technologies have been used to produce films, fibres, foams, sponges, aerogels, etc. Given their natural origin and high stiffness, these polymers have attracted a lot of attention not only in the biomedical and tissue engineering fields but also in areas such as pharmaceutics, cosmetics, agriculture, biosensors and water treatment.

Soares, P. I. P., C. A. T. Laia, A. Carvalho, L. C. J. Pereira, J. T. Coutinho, I. M. M. Ferreira, C. M. M. Novo, and J. P. Borges, "Iron oxide nanoparticles stabilized with a bilayer of oleic acid for magnetic hyperthermia and MRI applications", Appl Surf Sci, vol. 383, pp. 240-247, 2016. AbstractDOI

Iron oxide nanoparticles (Fe3O4, IONPs) are promising candidates for several biomedical applications such as magnetic hyperthermia and as contrast agents for magnetic resonance imaging (MRI). However, their colloidal stability in physiological conditions hinders their application requiring the use of biocompatible surfactant agents. The present investigation focuses on obtaining highly stable IONPs, stabilized by the presence of an oleic acid bilayer. Critical aspects such as oleic acid concentration and pH were optimized to ensure maximum stability. NPs composed of an iron oxide core with an average diameter of 9 nm measured using transmission electron microscopy (TEM) form agglomerates with an hydrodynamic diameter of around 170 nm when dispersed in water in the presence of an oleic acid bilayer, remaining stable (zeta potential of −120 mV). Magnetic hyperthermia and the relaxivities measurements show high efficiency at neutral pH which enables their use for both magnetic hyperthermia and MRI.

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.

Soares, P. I. P., A. I. Sousa, I. M. M. Ferreira, C. M. M. Novo, and J. P. Borges, "Towards the development of multifunctional chitosan-based iron oxide nanoparticles: Optimization and modelling of doxorubicin release", Carbohydr Polym, vol. 153, pp. 212-221, 2016. AbstractDOI

In the present work composite nanoparticles with a magnetic core and a chitosan-based shell were produced as drug delivery systems for doxorubicin (DOX). The results show that composite nanoparticles with a hydrodynamic diameter within the nanometric range are able to encapsulate more DOX than polymeric nanoparticles alone corresponding also to a higher drug release. Moreover the synthesis method of the iron oxide nanoparticles influences the total amount of DOX released and a high content of iron oxide nanoparticles inhibits DOX release. The modelling of the experimental results revealed a release mechanism dominated by Fickian diffusion.

Bianchi, C., J. Loureiro, P. Duarte, J. Marques, J. Figueira, I. Ropio, and I. Ferreira, "V2O5 Thin Films for Flexible and High Sensitivity Transparent Temperature Sensor", Advanced Materials Technologies, vol. 1, issue 6, pp. 1600077, 2016. AbstractDOI

This work reports the optimization of V2O5 Seebeck coefficient to obtain high sensitivity and transparent temperature sensors. It is observed that the film thickness plays a major role on the thermoelectric properties, together with the annealing step, obtaining a Seebeck coefficient of −690 μV K−1, for 75 nm thick V2O5 films deposited on glass, after an annealing step of 1 h at 773 K, in air. The V2O5 films are also deposited and optimized on polyimide substrates, but lower annealing temperature is required, 573 K for 3 h, to maintain the flexibility of the substrate and simultaneously high Seebeck coefficient, −591 μV K−1. These films are used in a simple design sensor and tested on the surface of a microfluidic channel (500 μm) made of polydimethylsiloxane, while having hot water flowing through it. The response time is below 1 s and the recovery time around 5 s.

Bianchi, C., L. M. Ferreira, J. Loureiro, A. Rodrigues, P. Duarte, A. C. Baptista, and I. M. Ferreira, "Vanadium Pentoxide Alloyed with Graphite for Thin-Film Thermal Sensors", J. Electron. Mater., vol. 45, issue 3, pp. 1987–1991, 2016. AbstractDOI

The thermoelectric (TE) properties of vanadium pentoxide (V2O5) alloyed with graphite (G) were studied as a function of its incorporation percentage. Variable weight percentages of graphite powder (0–50%) were added to V2O5 powder and their mixtures were evaporated by a thermal evaporation technique to form thin films with a thickness in the range of 30–80 nm. In the infrared wavelength region, the transmittance of the obtained films increased as the G percentage was increased, while in the visible range, it decreased with G up to 10%. The TE properties were improved when G was in the range of 10–30%, while it decreased for the other percentages: Seebeck coefficient (S) changed from 0.6 mV/K to 0.9 mV/K and was zero with a G of 50%; the electrical conductivity varied slightly from 5 (Ωm)−1 to 0.7 (Ωm)−1 while the mobility improved from 0.07 cm2/V s to 1.5 cm2/V s and the respective carrier concentration was reduced, from 1 × 1018 cm−3 to 4 × 1016 cm−3. These films were applied as temperature sensors evaluating the thermovoltage as a function of thermal gradient between two electrodes, in which one was maintained at room temperature.

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.

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.