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2021
Gavinho, Sílvia R., Manuel P. Graça, Pedro Prezas, João Borges Borges, Jorge Carvalho Silva, Eduardo Pires, Henrique Armês, and José Coucelo. "Antibacterial bioglass in dental implants: a canine clinical study." European Journal of Public Health 31 (2021): ckab120.006. AbstractWebsite

Background
Peri-implantitis is considered the most challenging biological complication in implantology, as untreated disease can progress and result in implant loss. Therefore, disease prevention is crucial in daily clinical practice. It has been reported that the use of bioactive glass, as an implant coating, can stimulate tissue integration and accelerate tissue regeneration. Besides these properties, it is possible to promote bacterial activity by inserting silver into the bioglass

Methods
Bioglass with composition 45S5 was synthesised by the fusion method, replacing the amount of Na2CO3 by AgNO3 (BG 2% wt). The implants were resealed by the CoBlast® technique. Clinical cases with pathology of the mandible/maxilla were selected and implants dimensioned for the canine bone structure were applied.

Results
Three months after implantation, imaging exams, namely CT scans, showed no signs of early rejection by septic or cytotoxic loss. No decrease or loss of peri-implant bone was observed. In all cases the implants remained without signs of instability, and with sufficient support for the application of the exo-prosthesis or dental crown. The results of histological analysis showed no signs of infection or osteolysis. The zone of peri-implant fibrosis was not observable in the samples, showing a good evolution in implant osteointegration.

Conclusions
The results show promising evidences for the use of this biomaterial as a coating, since aseptic rejection, later on, and that related to the shape and biomaterials used in the implant's design, usually begins during the first 3 months.

Gonçalves, Adriana, Filipe V. Almeida, João Paulo Borges, and Paula I. P. Soares. "Incorporation of Dual-Stimuli Responsive Microgels in Nanofibrous Membranes for Cancer Treatment by Magnetic Hyperthermia." Gels 7 (2021): 28. AbstractWebsite

The delivery of multiple anti-cancer agents holds great promise for better treatments. The present work focuses on developing multifunctional materials for simultaneous and local combinatory treatment: Chemotherapy and hyperthermia. We first produced hybrid microgels (MG), synthesized by surfactant-free emulsion polymerization, consisting of Poly (N-isopropyl acrylamide) (PNIPAAm), chitosan (40 wt.%), and iron oxide nanoparticles (NPs) (5 wt.%) as the inorganic component. PNIPAAm MGs with a hydrodynamic diameter of about 1 μm (in their swollen state) were successfully synthesized. With the incorporation of chitosan and NPs in PNIPAAm MG, a decrease in MG diameter and swelling capacity was observed, without affecting their thermosensitivity. We then sought to produce biocompatible and mechanically robust membranes containing these dual-responsive MG. To achieve this, MG were incorporated in poly (vinyl pyrrolidone) (PVP) fibers through colloidal electrospinning. The presence of NPs in MG decreases the membrane swelling ratio from 10 to values between 6 and 7, and increases the material stiffness, raising its Young modulus from 20 to 35 MPa. Furthermore, magnetic hyperthermia assay shows that PVP-MG-NP composites perform better than any other formulation, with a temperature variation of about 1 °C. The present work demonstrates the potential of using multifunctional colloidal membranes for magnetic hyperthermia and may in the future be used as an alternative treatment for cancer.

2019
Khili, Faouzia, João Borges Borges, Pedro L. Almeida, Rabah Boukherroub, and Amel Dakhlaoui Omrani. "Extraction of Cellulose Nanocrystals with Structure I and II and Their Applications for Reduction of Graphene Oxide and Nanocomposite Elaboration." Waste and Biomass Valorization 10 (2019): 1913-1927. AbstractWebsite

The aim of the present study is to investigate the effect of the hydrolysis process on the properties of nanocrystalline cellulose (NCC) isolated from different precursors and the subsequent use of the extracted NCC for the reduction of graphene oxide (GO). The raw materials (almond and peanut shells) chosen for the isolation of cellulose were selected on the basis of their abundance and their poorly investigation in the production of NCC. Microcrystalline cellulose (MCC) was firstly extracted by alkali and bleaching treatments, then hydrolyzed under different processes to produce NCC polymorphs with structure I (NCC-I) and NCC structure II (NCC-II). The Fourier transform infrared spectroscopy, the X-ray diffraction (XRD) and the 13C NMR studies of the alkali and bleached products confirmed the formation of cellulose type I with high purity and good crystallinity, while scanning electron microscopy (SEM) showed micrometric fibers with lengths reaching 80 µm. Sulfuric acid treatment of these microfibers results in NCC type I or II, depending on the hydrolysis process. SEM of the NCC samples exhibited nanorods with diameter and aspect ratio in the range of 20–40 and 20–25 nm, respectively. Thermogravimetric analysis (TGA) of the MCC and NCC products indicated stable materials with a degradation temperature reaching 240 and 200 °C for MCC and NCC, respectively. The other part of our work concerns the use of the obtained cellulose nanocrystals (type II) for the preparation of reduced graphene oxide composite (NCC/RGO), to demonstrate the reducing properties of the isolated NCCII.

Marques, Ana, Davide Miglietta, G. Gaspar, Ana Catarina Baptista, A. Gaspar, P. Perdigão, Iris Soares, Catarina Bianchi, David Sousa, Bruno Morais M. Faustino, V. S. Amaral, T. Santos, A. P. Gonçalves, R. C. da Silva, Fabrizio Giorgis, and Isabel Ferreira. "Synthesis of thermoelectric magnesium-silicide pastes for 3D printing, electrospinning and low-pressure spray." Materials for Renewable and Sustainable Energy 8 (2019): 21. AbstractWebsite

In this work, eco-friendly magnesium-silicide (Mg2Si) semiconducting (n-type) thermoelectric pastes for building components concerning energy-harvesting devices through 3D printing, spray and electrospinning were synthetized and tested for the first time. The Mg2Si fine powders were obtained through the combination of ball milling and thermal annealing under Ar atmosphere. While the latter process was crucial for obtaining the desired Mg2Si phase, the ball milling was indispensable for homogenizing and reducing the grain size of the powders. The synthetized Mg2Si powders exhibited a large Seebeck coefficient of ~ 487 µV/K and were blended with a polymeric solution in different mass ratios to adjust the paste viscosity to the different requirements of 3D printing, electrospinning and low-pressure spray. The materials produced in every single stage of the paste synthesis were characterized by a variety of techniques that unequivocally prove their viability for producing thermoelectric parts and components. These can certainly trigger further research and development in green thermoelectric generators (TEGs) capable of adopting any form or shape with enhanced thermoelectric properties. These green TEGs are meant to compete with common toxic materials such as Bi2Te3, PbTe and CoSb that have Seebeck coefficients in the range of ~ 290–700 μV/K, similar to that of the produced Mg2Si powders and lower than that of 3D printed bulk Mg2Si pieces, measured to be ~ 4866 μV/K. Also, their measured thermal conductivities proved to be significantly lower (~ 0.2 W/mK) than that reported for Mg2Si (≥ 4 W/mK). However, it is herein demonstrated that such thermoelectric properties are not stable over time. Pressureless sintering proved to be indispensable, but difficultly achievable by long thermal annealing (even above 32 h) in inert atmosphere at 400 °C, at least for bulk Mg2Si pieces constituted by a mean grain size of 2–3 μm. Hence, for overcoming this sintering challenge and become the silicide’s extrusion viable in the production of bulk thermoelectric parts, alternative pressureless sintering methods will have to be further explored.

2017
Soares, Paula I. P., Coro Echeverria, Ana Catarina Baptista, Carlos João, Susete Fernandes, Ana Almeida, Jorge Carvalho Silva, Maria Helena Godinho, and João Paulo Borges. "Hybrid polysaccharide-based systems for biomedical applications." In Hybrid Polymer Composite Materials: Applications, edited by Manju Kumari Thakur, Vijay Kumar Thakur and Asokan Pappu, 107-149. USA: Woodhead Publishing, Elsevier, 2017. Abstract

Hybrid materials have been widely studied for structural applications. Polysaccharide-based fibers, especially cellulosic fibers, have been explored in the last two decades as substitutes of the traditional reinforcements made of glass or carbon fibers due to their mechanical properties. However, their biocompatibility, biodegradability, and chemistry have attracted the researchers and new developments in the field of smart and functional materials arise in diverse applications. This chapter will focus on the biomedical applications of polysaccharide-based smart and functional materials, namely those concerning biosensors and actuators, theranostic systems, and tissue-engineering applications. Special attention will be given to cellulose- and chitin/chitosan-based hybrid materials because these are the two most abundant polysaccharides and probably the most promising for the development of hybrid materials for biomedical applications. Biomimetic strategies for the development of smart and functional hybrid materials will also be highlighted.

Lakhdar, Allagui, João Paulo Borges, Abdesslam Amara, and Amel Omrani. "Template-free synthesis of sub-micrometric cobalt fibers with controlled shape and structure. Characterization and magnetic properties." Journal of Magnetism and Magnetic Materials 425 (2017): 6-11. AbstractWebsite

Sub-micrometric Co fibers were prepared via a modified polyol process at 90 °C under an external magnetic field of about 550 Oe, using ethelyne glycol as solvent and hydrazine as reducing agent. The structure, the size and the morphology of the as-elaborated products were highly controlled through properly monitoring the synthesis parameters (amount of NaOH added, the amount of the reducing agent, precursor’ concentration and precursors mixing protocol). The XRD characterization confirmed the formation of pure cobalt powders with either hexagonal compact (hcp) or face-centered-cubic (fcc) structure depending on the concentration of the metal precursor and sodium hydroxide. The scanning electron microscopy observations of the powders shows sub-micrometric fibers with about 0.4–0.6 µm in diameter and a length that could reach 15 µm. Fibers prepared at high reducing ratio were constituted of flower-like spheres that coalesce in the direction of the applied magnetic field. For their high contact surface, these fibers offer new opportunities for catalysis applications. The hysteresis loop measurements show an enhancement of the Hc of the as-obtained fibers compared to their bulk counterparts and permit to confirm the relationship between the structure and the magnetic properties of the materials.

2016
João, Carlos, Rute Almeida, Jorge Carvalho Silva, and João Paulo Borges. "A simple sol-gel route to the construction of hydroxyapatite inverted colloidal crystals for bone tissue engineering." Materials Letters 185 (2016): 407-410. AbstractWebsite

Hydroxyapatite (HAp) scaffolds with uniform pore size and interconnected pore network were constructed based on the inverted colloidal crystal (ICC) geometry and a simple sol-gel formulation. Monodisperse polystyrene microspheres were self-assembled and annealed into a hexagonal close packed structure. HAp sol-gel was infiltrated in this template followed by thermal treatment for simultaneous HAp matrix sintering and polymeric colloidal crystal calcination. The resultant ICC scaffolds exhibit an ordered architecture that was able to offer a favorable environment for human osteoblasts adhesion and proliferation, an essential feature for bone ingrowth in tissue engineering applications.

2015
Baptista, Ana Catarina, Alexandre Botas, Ana Almeida, Ana Nicolau, Bruno Falcão, Manuel Soares, Joaquim Pratas Leitão, Rodrigo Martins, João Paulo Borges, and Isabel Ferreira. "Down conversion photoluminescence on PVP/Ag-nanoparticles electrospun composite fibers." Optical Materials 39 (2015): 278-281. AbstractWebsite

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.

Mano, Francisca, Ivo Aroso, Susana Barreiros, João Paulo Borges, Rui Reis, Ana Rita Duarte, and Alexandre Paiva. "Production of Poly(vinyl alcohol) (PVA) Fibers with Encapsulated Natural Deep Eutectic Solvent (NADES) Using Electrospinning." ACS Sustainable Chemistry & Engineering 3 (2015): 2504-2509. AbstractWebsite

Functionalized electrospun fibers are of great interest for biomedical applications such as in the design of drug delivery systems. Nevertheless, in some cases the molecules of interest have poor solubility in water or have high melting temperatures. These drawbacks can be overcome using deep eutectic solvents. In this work, poly(vinyl alcohol) (PVA), a common biodegradable biopolymer, was used to produce new functionalized fibers with the eutectic mixture choline chloride:citric acid in a molar ratio of (1:1) ChCl:CA (1:1), which was used as a model system. Fibers were produced from an aqueous solution with 7.8% (w/v) and 9.8% (w/v) of 95% hydrolyzed PVA and a 2% (v/v) of ChCl:CA (1:1). Smooth, uniform fibers with an average diameter of 0.4 μm were obtained with a content of 19.8 wt % of ChCl:CA (1:1) encapsulated.

2014
Soares, Paula I. P., Isabel Ferreira, and João Paulo Borges. "Application of Hyperthermia for Cancer Treatment: Recent Patents Review." In Topics in Anti-Cancer Research, Vol. 3, edited by Atta-ur-Rahman and Khurshid Zaman, 342-383. Bentham Science Publishers, 2014. Abstract

Cancer is one of the main causes of death in the world and its incidence increases every day. Current treatments are insufficient and present many breaches. Hyperthermia is an old concept and was early established as a cancer treatment option, mainly in superficial cancers. More recently, the concept of intracellular hyperthermia emerged wherein magnetic particles are concentrated at the tumor site and remotely heated using an applied magnetic field to achieve hyperthermic temperatures (42-45ºC). Many patents have been registered in this area since the year 2000. This chapter presents the most relevant information organized in two main categories according to the use or not of nanotechnology. The patents without nanotechnology were divided into the following subcategories: 1) external Radio-Frequency devices; 2) hyperthermic perfusion; 3) frequency enhancers; 4) applying heat to the target site using a catheter; and 5) injection of magnetic and ferroelectric particles. The patents with nanotechnology were divided into three subcategories: 1) hyperthermia devices; 2) nanoparticles; and 3) nanostructures. The use of magnetic nanoparticles is a very promising treatment approach since it may be used for diagnostic and treatment. Magnetic nanoparticle could be applied to detect and diagnose the tumor and to carry a pharmacological active drug to be delivered in the tumor site or apply hyperthermia through an external magnetic field.

Soares, Paula I. P., Ana Alves, Laura Pereira, Joana Coutinho, Isabel Ferreira, Carlos Novo, and João Paulo Borges. "Effects of surfactants on the magnetic properties of iron oxide colloids." Journal of Colloid and Interface Science 419 (2014): 46-51. AbstractWebsite

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.

2012
Pimenta, Andreia F. R., Ana Catarina Baptista, Tânia Carvalho, Pedro Brogueira, Nuno Lourenço, Carlos Afonso, Susana Barreiros, Pedro Vidinha, and João Paulo Borges. "Electrospinning of Ion Jelly fibers." Materials Letters 83 (2012): 161-164. AbstractWebsite

Ion Jelly materials combine the chemical versatility and conductivity of an ionic liquid (IL) with the morphological versatility of a biopolymer (gelatin). They exhibit very interesting properties, such as conductivities up to 10− 4 S cm− 1, and high thermostability up to 180 °C, and have been used successfully to design electrochromic windows. In this work we report on the preparation of Ion Jelly fibers through electrospinning in order to obtain high surface area conductive materials. We have used the IL 1-(2-hydroxyethyl)-3-methyl-imidazolium tetrafluoroborate ([C2OHmim]BF4), which exhibits conveniently high ionic conductivity (over 10− 3 S cm− 1) and electrochemical stability (electrochemical window over 6.0 V). The morphology of the obtained fibers was quantified using Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM). We found that on average the effect of the IL on fiber diameter differs for lower and higher IL concentrations and that this effect was correlated with the initial conductivity and viscosity of Ion Jelly electrospinning solution. Moreover we also found that conductivities of Ion Jelly fibers are of the same order of magnitude as the conductivities of Ion Jelly dense films (~ 10− 4 S cm− 1). To the best of our knowledge, this is the first report on the incorporation of an IL into gelatin fibers using electrospinning. This opens up new opportunities for the application of gelatin fibers in electrochemical and biomedical devices.

2009
Almeida, Pedro L., Sudarshan Kundu, João Paulo Borges, Maria Helena Godinho, and Joao L. Figueirinhas. "Electro-optical light scattering shutter using electrospun cellulose-based nano-and microfibers." Applied Physics Letters 95 (2009): 043501. AbstractWebsite

Electrospun cellulose-based nano and microfibers and a nematic liquid crystal are used to assemble an electro-optical (EO) light-scattering device that shows enhanced characteristics when compared to similar devices. Based on the controlled scattering of light in the composite system, the device can achieve light transmission coefficients tunable from 1% up to around 89%. Simulation of the EO behavior indicates that the roughness of the polymer-liquid crystal interface is crucial for the optical performance of the device.