Close-to-native bone repair via tissue-engineered endochondral ossification approaches

In order to solve the clinical challenges related to bone grafting, several tissue engineering (TE) strategies have been proposed to repair critical-sized defects. Generally, the classical TE approaches are designed to promote bone repair via intramembranous ossification. Although promising, strategies that direct the osteogenic differentiation of mesenchymal stem/stromal cells are usually characterized by a lack of functional vascular supply, often resulting in necrotic cores. A less explored alternative is engineering bone constructs through a cartilage-mediated approach, resembling the embryological process of endochondral ossification. The remodeling of an intermediary hypertrophic cartilaginous template triggers vascular invasion and bone tissue deposition. Thus, employing this knowledge can be a promising direction for the next generation of bone TE constructs. This review highlights the most recent biomimetic strategies for applying endochondral ossification in bone TE while discussing the plethora of cell types, culture conditions, and biomaterials essential to promote a successful bone regeneration process.publishe

Carbon dioxide emissions and heavy metal contamination analysis of stone mastic asphalt mixtures produced with high rates of different waste materials

The incorporation of waste materials in asphalt mixtures has driven several studies mainly focused on improving their mechanical performance while minimizing the use of virgin materials. However, these could only be considered cleaner solutions for road paving works if their production and application do not present additional risks for human health and the environment. Therefore, this study aims at assessing the carbon dioxide emissions and possible leachates of stone mastic asphalt mixtures produced with high rates of different waste materials for binder modification or material recycling. Thus, a chemical analysis of eluates that were in contact with those mixtures and an estimation of the carbon dioxide emissions associated with their production and transportation were carried out under different scenarios. In conclusion, these mixtures comply with the established specifications for hazardous leachates. The addition of waste materials to these mixtures decreases carbon dioxide emissions, especially for recycled stone mastic asphalt mixtures with 50% reclaimed asphalt pavement material and bitumens modified with waste materials. Thus, the studied mixtures are innovative solutions for future use in pavement maintenance and rehabilitation operations, in line with the circular economy concept.The authors gratefully acknowledge the funding by the Portuguese Government and EU/FSE within a Portuguese Foundation for Science and Technology (FCT) Ph.D. grant (SFRH/BD98379/2013), in the scope of POPH/QREN

Mechanical, surface and environmental evaluation of stone mastic asphalt mixtures with advanced asphalt binders using waste materials

The reuse of waste materials in asphalt mixtures has been recently investigated, in order to develop new sustainable solutions for the road-paving industry. Such materials should improve the mechanical performance and provide safe/comfortable pavement surface courses for road users, without compromising their environmental performance. Thus, the aim of this study is to evaluate the mechanical, surface and environmental properties of stone mastic asphalt (SMA) mixtures produced with forward-looking asphalt binders incorporating waste materials. These binders were designed to maximise the waste material content using motor oil, high-density polyethylene, styrene?butadiene?styrene and crumb rubber, while performing so well as a commercial modified bitumen. Finally, the overall performance of the SMA mixtures produced with the selected binders was evaluated. It was concluded that these mixtures improve the water sensitivity, fatigue cracking and permanent deformation performance. The requirements for macrotexture, skid resistance and presence of heavy metals in leachates of these mixtures were similarly fulfilled. Thus, this work shows that new asphalt mixtures with waste materials can be used in road-paving works to improve the performance without compromising human and environmental safety.Portuguese Government and EU/FSE within a PhD fellowship (SFRH/BD98379/2013) of the FCT, in the scope of POPH/QREN, by ERDF (European Regional Development Fund) funds through the Competitiveness Factors Operational Programme (COMPETE)info:eu-repo/semantics/publishedVersio

Valorização de resíduos plásticos na modificação de betumes para pavimentos rodoviários

Com o aumento do tráfego rodoviário são colocadas maiores exigências aos pavimentos, surgindo a necessidade de melhorar o seu desempenho. Um método que pode melhorar significativamente a qualidade dos pavimentos flexíveis é a adição de polímeros aos ligantes/misturas betuminosas. Assim, foram produzidos ligantes modificados com polímeros reciclados, em diferentes condições, cujo desempenho foi comparado com o de ligantes convencionais e de um ligante modificado comercial. Os resultados dos ensaios laboratoriais serão utilizados na seleção de resíduos plásticos e das condições de produção do betume modificado para otimizar o seu comportamento, salientando-se que este estudo procura promover a reutilização de resíduos de uma forma mais ecológica e económica.Financiado por Fundos FEDER através do Programa Operacional Fatores de Competitividade – COMPETE e por Fundos Nacionais através da FCT – Fundação para a Ciência e a Tecnologia no âmbito do projeto PLASTIROADS (PTDC/ECM/119179/2010) e do projeto estratégico UI 4047 – 2011-2012

Effects of Green Tea Marinade in the Bioaccessibility of Tonalide and Benzophenone 3 in Cooked European Seabass

The authors acknowledgment Fundação para a Ciência e Tecnologia: NORTE-01-0145-FEDER-000041; IM acknowledges FCT for Ph.D. Grant DFA/BD/4413/2020. Publisher Copyright: © 2022 by the authors.Fish consumption is an indicator of human exposure to personal care products (PCP) such as tonalide (AHTN) and benzophenone 3 (BP3). Although most fish consumed is cooked, the impact of cooking procedures on PCP levels is difficult to evaluate. Hence, the aim of this work was to provide thorough information on the stability and bioaccessibility of AHTN and BP3 upon cooking and in vitro digestion. A green tea (Camellia sinensis) marinade, rich in polyphenol, was used as mitigating strategy to reduce these contaminants. Roasting and frying reduced AHTN and BP3 levels in European seabass (Dicentrarchus labrax) spiked samples. Additionally, the green tea marinade promoted a reduction of up to 47% AHTN and 35% BP3. Bioaccessibility of AHTN was higher (up to 45%), and increased with the use of green tea marinades. BP3 showed a bioaccessibility below 19% in all cooked samples. Overall, a decrease in PCP levels was observed after cooking; this decrease was even more pronounced when marination was previously used. However, this decrease is cancelled out by the fact that the bioaccessible fraction of the contaminants increases in an inverse way; therefore, none of these processes can be considered a mitigating alternative.publishersversionpublishe

Utilization of waste materials to improve asphalt mixtures performance

This study aims to develop an innovative bitumen with large quantities of waste materials to improve asphalt mixtures performance. Different amounts of waste motor oil and waste HDPE were added to a new bitumen. The bitumen modified with 10% of waste motor oil and 5% of HDPE showed promising characteristics (high softening point temperatures and penetration slightly higher than the conventional bitumen). After the selection of the most promising modified bitumen, three asphalt mixtures were produced with different bitumens (namely conventional bitumen, commercial modified bitumen and the selected modified bitumen). Beyond that, this modified bitumen improved some mechanical characteristics of the asphalt mixture where it was used, in comparison to conventional and modified asphalt mixtures.Portuguese Government and EU/FSE within a PhD fellowship (SFRH/BD98379/2013) of the FCT, in the scope of POPH/QREN, by FEDER through the Competitiveness Factors Operational Programme (COMPETE) and by national funds through the Portuguese Foundation for Science and Technology (FCT) in the scope of PLASTIROAD Project (PTDC/ECM/119179/2010

Bithiophene azo dyes bearing thiazole, benzothiazole and thiadiazole heterocycles: synthesis and comparative study of their photochromic properties

Although a large variety of diarylazo compounds are used in the design of optical materials, only a few reports concerning the photoisomerization of heterocyclic azo dyes can be found in the literature. In the last years our group reported for the first time the synthesis and characterization of heterocyclic azo dyes bearing thiophene and pyrrole moieties as thermally stable conducting materials, solvatochromic probes and nonlinear optical systems. The E/Z isomerizable N=N double bond within a conducting chain can work as molecular switch, making these (hetero)aryl azo systems promising candidates as photochromic materials [1-6]. As part of our continuing interest in heterocyclic azo dyes for optical applications we report here the synthesis of dithiazole azo dyes 4 using as coupling components bithiophene and thiadiazolyldiazonium salts and the comparative study of the photochromic properties of 4 classes of bithiophene azo dyes 1-4. This study reveals that the kinetics of the E-Z transformation of these systems is strongly influenced by the electronic nature of the heterocyclic diazene moiety as well as its position on the bithiophene system. Moreover, for benzothiazole 3 and thiadiazole 4 azo dyes the switching between the two photoisomers can be performed in 3 seconds with a significant conversion of the trans-isomer to the thermal unstable cis-isomer (19-21%) showing that they could be used as efficient photochromic materials. Thanks are due to the Fundação para a Ciência e Tecnologia (Portugal) and FEDER-COMPETE for financial support through the Centro de Química - Universidade do Minho, Projects PTDC/QUI/66251/2006 (FCOMP-01-0124-FEDER-007429), PEst-C/QUI/UI0686/2011 (F-COMP-01-0124-FEDER-022716) and a PhD grant to M. C. R. Castro (SFRH/BD/78037/2011). [1] Coelho, P. J.; Castro, M. C. R.; Fonseca, A. M. C.; Raposo, M.M.M. Dyes Pigments 2012, 92, 745. [2] Raposo, M. M. M.; Castro, M. C. R.; Schellenberg, P.; Fonseca, A. M. C.; Belsley, M. Tetrahedron 2011, 67, 5189. [3] Raposo, M. M. M.; Fonseca, A. M. C.; Castro, M. C. R.; Belsley, M.; Cardoso, M. F. S.; Carvalho, L. M.; Coelho, P. J. Dyes Pigments 2011, 91, 62. [4] Raposo, M. M. M.; Castro, M. C. R.; Belsley, M.; Fonseca, A. M. C. Dyes Pigments 2011, 91, 454. [5] Coelho, P. J.; Carvalho, L. M.; Moura, J. C. V. P.; Raposo, M. M. M. Dyes Pigments 2009, 82, 130. [6] Coelho, P. J.; Carvalho, L. M.; Fonseca, A. M. C.; Raposo, M. M. M. Tetrahedron Lett 2006, 47, 3711

Atmospheric plasma and UV polymerisation for developing sustainable anti-adhesive polyethylene terephthalate (PET) surfaces

Enhancing the hydrophilicity of polymeric materials is an important step for achieving anti-adhesiveness. Thus, in this study, atmospheric plasma as a pre-treatment was combined with a UV grafting process to obtain a durable surface modification on polyethylene terephthalate (PET). The most promising conditions for the atmospheric plasma process were found to be 15 kW power and 4 m/min speed, leading to a contact angle reduction from 70 ± 6° to approximately 30°. However, it was observed that these values increased over time due to the ageing and washing of the PET surface, ultimately causing it to recover its initial contact angle. Therefore, the plasma-pre-treated PET samples were further modified through a UV grafting process using sodium acrylate (NaAc) and 3-sulfopropyl acrylate potassium salts (KAc). The grafted acrylate PET samples exhibited contact angles of 8 ± 3° and 28 ± 13° for NaAc and KAc, respectively, while showing durability in ageing and washing tests. The dry film thicknesses for both samples were found to be 28 ± 2 μm. Finally, the anti-adhesive properties of the NaAc- and KAc-treated surfaces were evaluated using an Escherichia coli expressing YadA, an adhesive protein from Yersinia. The modified PET surfaces were highly effective in reducing bacterial adhesion by more than 90%.This work was supported by the ViBrANT project, which received funding from the EU Horizon 2020 Research and Innovation Programme under Marie Sklowdowska-Curie (grant agreement no. 765042), and the Portuguese Foundation for Science and Technology (FCT) (grant number UIDB/04469/2020).info:eu-repo/semantics/publishedVersio

Enhancement of the photochromic switching speed of bithiophene azo dyes

A series of heteroaryl substituted bithiophene azo dyes in solution were irradiated with visible light to promote the azo E–Z isomerization and then the kinetics of the thermal Z–E back reaction was studied. The speed of this process is strongly influenced by the nature of the aromatic ring linked to the N=N function.While thiazole bithiophene azo dyes exhibit high switching speeds between the two isomers, but limited interconversion, for benzothiazole and substituted thiadiazole bithiophene azo dyes the switching between the two photoisomers can be performed in 3 s with a significant conversion of the transisomer to the thermal unstable cis-isomer (19–21%) and therefore a notable variation of the visible spectrum is observed.Fundação para a Ciência e a Tecnologia (FCT

Modification of PET surfaces with Gum Arabic towards its bacterial anti-adhesiveness using an experimental factorial design approach

Bacterial adhesion onto hospital material surfaces still represents a big healthcare issue, being preventive measures required to mitigate this problem, such as increasing material surface hydrophilicity. In the present study, gum Arabic, a hydrophilic polysaccharide, was used to modify the surface of polyethylene terephthalate (PET). Initial water contact angle (WCA) and WCA after several washing cycles were studied as response variables by a 24 full factorial design. Several reaction parameters, such as contact time between gum Arabic and PET, gum Arabic concentration, curing temperature and curing time for PET modification were investigated. The most significant parameters were found to be the curing temperature and curing time. The optimized parameters led to a WCA reduction from 70° to 27°. The modified PET samples were characterized using several techniques including AFM, colorimetric, ATR-FTIR and contact angle which further confirmed a successful surface modification. Furthermore, bacterial adhesion assays have clearly shown that the treated PET material was highly effective in preventing the bacterial adhesion of Escherichia coli expressing YadA, an adhesive protein from Yersinia so-called Yersinia adhesin. The use of design of experiments techniques allowed for successfully attaining a PET material with a high bacterial anti-adhesiveness, using a simple grafting approach.This work was supported by the ViBrANT project that received funding from the EU Horizon 2020 Research and Innovation Programme under the Marie Sklowdowska-Curie, Grant agreement no 765042 and the Portuguese Foundation for Science and Technology (FCT) under the scope of the strategic funding of UIDB/04469/2020.info:eu-repo/semantics/publishedVersio