Preparation of plasmonic Au-TiO2 thin films on a transparent polymer substrate

In this work, plasmonic thin films composed of Au nanoparticles embedded in a TiO2 matrix were prepared in a transparent polymer substrate of poly(dimethylsiloxane) (PDMS). The thin films were deposited by reactive DC magnetron sputtering, and then subjected to heat treatment up to 150 °C in order to promote the growth of the Au nanoparticles throughout the TiO2 matrix. The transmittance spectrum of the thin films was monitored in situ during the heat treatment, and the minimum time required to have a defined localized surface plasmon resonance (LSPR) band was about 10 min. The average size of Au nanoparticles was estimated to be about 21 nm—the majority of them are sized in the range 10–40 nm, but also extend to larger sizes, with irregular shapes. The refractive index sensitivity of the films was estimated by using two test fluids (H2O and DMSO), and the average value reached in the assays was 37.3 ± 1.5 nm/RIU, resulting from an average shift of 5.4 ± 0.2 nm. The results show that it is possible to produce sensitive plasmonic Au-TiO2 thin films in transparent polymer substrates such as PDMS, the base material to develop microfluidic channels to be incorporated in LSPR sensing systems.This research was funded by the Portuguese Foundation for Science and Technology (FCT), co-financed by European Regional Development Fund (ERDF), in the framework of the Strategic Funding, grant number UID/FIS/04650/2019; also by the project NANOSENSING, grant number POCI-01-0145-FEDER-016902 and FCT reference PTDC/FIS-NAN/1154/2014; and by the project NANO4BIO, grant number POCI-01-0145-FEDER-032299 and FCT reference PTDC/FIS-MAC/32299/2017.Joel Borges acknowledges the Portuguese Foundation for Science and Technology (FCT) for his Researcher Contract from project NANO4BIO (grant number POCI-01-0145-FEDER-032299 and FCT reference PTDC/FIS-MAC/32299/2017). Diana I. Meira acknowledges FCT for her PhD Scholarship, SFRH/BD/143262/2019. Marco S. Rodrigues acknowledges FCT for his PhD Scholarship, SFRH/BD/118684/2016. Cláudia Lopes acknowledges her post-doctoral fellowship from project NANOSENSING (POCI-01-0145-FEDER-016902 and FCT reference PTDC/FIS-NAN/1154/2014)

Using MACBETH with the choquet integral fundamentals to model interdependencies between elementary concerns in the context of risk management

Effective risk management typically requires the evaluation of multiple consequences of different sources of risk, and multicriteria value models have been used for that purpose. The value of mitigating a risk impact is often considered by risk managers as dependent on the levels of other impacts, therefore there is a need for procedures to identify and model these interactions within a value measurement framework. The Choquet Integral (CI) has been used for this purpose, and several studies in the performance measurement literature have combined the 2-additive CI operator with the MACBETH approach to model interdependencies in real contexts. In this paper, we propose an alternative procedure to model interdependencies and determine the CI parameters from one single MACBETH global matrix. The procedure is illustrated with the construction of a descriptor of impacts to evaluate the risk impacts at ALSTOM Power. The paper further explains the questioning protocol to apply the proposed procedure, as well as how decision-makers can interpret the CI parameters

Screening of perfused combinatorial 3D microenvironments for cell culture

Biomaterials combining biochemical and biophysical cues to establish close-to-extracellular matrix (ECM) models have been explored for cell expansion and differentiation purposes. Multivariate arrays are used as material-saving and rapid-to-analyze platforms, which enable selecting hit-spotted formulations targeting specific cellular responses. However, these systems often lack the ability to emulate dynamic mechanical aspects that occur in specific biological milieus and affect physiological phenomena including stem cells differentiation, tumor progression, or matrix modulation. We report a tailor-made strategy to address the combined effect of flow and biochemical composition of three-dimensional (3D) biomaterials on cellular response. We suggest a simple-to-implement device comprising (i) a perforated platform accommodating miniaturized 3D biomaterials and (ii) a bioreactor that enables the incorporation of the biomaterial-containing array into a disposable perfusion chamber. The system was upscaled to parallelizable setups, increasing the number of analyzed platforms per independent experiment. As a proof-of-concept, porous chitosan scaffolds with 1 mm diameter were functionalized with combinations of 5 ECM and cell-cell contact-mediating proteins, relevant for bone and dental regeneration, corresponding to 32 protein combinatorial formulations. Mesenchymal stem cells adhesion and production of an early osteogenic marker were assessed on-chip on static and under-flow dynamic perfusion conditions. Different hit-spotted biomaterial formulations were detected for the different flow regimes using direct image analysis. Cell-binding proteins still poorly explored as biomaterials components amelogenin and E-cadherin - were here shown as relevant cell response modulators. Their combination with ECM cell-binding proteins - fibronectin, vitronectin, and type 1 collagen - rendered specific biomaterial combinations with high cell adhesion and ALP production under flow. The developed versatile system may be targeted at wM.B. Oliveira acknowledges the financial support from Portuguese Foundation for Science and Technology- FCT (Grant SFRH/BPD/111354/2015). This work was developed within the scope of the projects CICECO-Aveiro Institute of Materials, POCI-01-0145-FEDER-007679 (FCT Ref. UID/CTM/50011/2013) and IPC/i3N Minho (FCT Ref. UID/CTM/50025/2013), financed by national funds through the FCT/MEC and when appropriate co-financed by FEDER under the PT2020 Partnership Agreement. This work was also supported by European Research Council grant agreement ERC-2014-ADG-669858 (project ATLAS)

Evaluation of the potential of fucoidan-based microparticles for diabetes treatment

Abstract INTRODUCTION: Marine organisms have in their constitution materials with a wide range of properties and characteristics inspiring their application within the biomedical field. One important example is fucoidan (Fu), an underexploited sulfated polysaccharide extracted from the cell wall of the brown seaweeds, with high solubility in water1. Fucoidan is composed of L- fucose and glucuronic acid including sulfate groups and has important bioactive properties such as antioxidative, anticoagulant, anticancer and in the reduction of blood glucose1,2. In this work, the biomedical potential of fucoidan was assessed by processing modified fucoidan (MFu) into microparticles by photocrosslinking using superhydrophobic surfaces and visible light3,4. Biological performance on the developed constructs using human pancreatic beta cells is currently under investigation. METHODS: To design the materials structures, fucoidan was modified by methacrylation reaction3. Briefly, Fu aqueous solution 4% w/v was mixed with methacrylated anhydride (MA) in volume of 12% v/v at 50oC to react for 6h. Further, MFu particles with and without insulin (0.5% w/v) were produced by pipetting a solution of 5% MFu v/v with triethanolamine and eosin-y (photoinitiators) onto superhydrophobic surfaces4 (Fig. 1A) and then photocrosslinking using visible light4. MFu and developed particles were characterized using 1HNMR, turbidimetry and SEM to assess their chemistry and morphology, respectively. Moreover, the insulin release was evaluated in phosphate buffered saline (PBS) solution at pH 7and simulated intestinal fluid (SIF) at pH 5. The ability of the developed materials to support adhesion and proliferation of cells was assessed by suspension culture of human pancreatic cells 1.1B4 (3.5x105 cells/ml) in contact with MFu microparticles during up to 7 days. RESULTS: The chemical modification performed on Fu was confirmed by the presence of vinyl and additional methyl peaks in the 1HNMR of modified fucoidan, not present in Fu spectrum. Methacrylated fucoidan was obtained with a methacrylation degree of 17%. The produced fucoidan particles have round shape and average diameter of 1.53 mm (Fig. 1B). The insulin release in PBS and SIF demonstrate that the particles can release insulin in a sustained manner under the studied period. It seems that the insulin release is slower for SIF (pH5, Fig. 1C), than for PBS. The biological tests regarding the culture of pancreatic beta cells demonstrate that cells show a round-like shape and tend to form pseudo-islets during the culture period studied (Fig. 1D). DISCUSSION & CONCLUSIONS: This work demonstrates the successful production of fucoidan- based-microparticles through the methacrylation of fucoidan, using visible light and superhydrophobic surfaces. The covalent crosslinking methacrylated fucoidan through visible light represents a promising method to obtain biocompatible fucoidan particles with a uniform round shape. The obtained insulin release profiles are sensitive to different pH (pH7 and pH5), mimicking the normal physiological pathway for insulin release. Furthermore, the results suggest these systems could be used for treatment of type I diabetes mellitus as they sustain beta cells viability and proliferation. The response also suggested, that the MFu particles could be a good candidate as drug delivery vehicles for the diabetes mellitus treatment. REFERENCES: 1 Silva TH et al (2012), Biomatter 2(4): 278:289. 2Sezer Alidemir et al (2011), Fucoidan: A versatile biopolymer for biomedical applicatons (Springer Ber.Heid).pp377-406. 3Mihaila S.et al (2013), Adv. Health. Mat. 2(6): 895-907. 4Rial Hermida et al, Acta Biomater.(2014) 10(10) 4314-4322. ACKNOWLEDGEMENTS: This work was partially funded by projects 0687_NOVOMAR_1_P (POCTEP), CarbPol_u_Algae (EXPL/MAR- BIO/0165/2013), ComplexiTE (ERC-2012-ADG 20120216-321266). Portuguese Foundation for Science and Technology is also gratefully acknowledged for doctoral grants of L. Reys and N. Oliveira and post- doctoral grants of S.S. Silva and D. Soares da Costafunded by projects 0687_NOVOMAR_1_P (POCTEP), CarbPol_u_Algae (EXPL/MARBIO/0165/2013) , ComplexiTE(ERC-2012-ADG 20120216-321266). Portuguese Foundation for Science and Technologyinfo:eu-repo/semantics/publishedVersio

Process simulation and techno-economic assessment for direct production of advanced bioethanol using a genetically modified Synechocystis sp.

ABSTRACT: A techno-economic assessment for the direct production of ethanol using a genetically-modified microalgae has been studied. It was considered two main scenarios for process modelling: i) bioenergy-driven microalgae plant, i.e., focused on the production of fuel-grade ethanol and biogas for CHP and, ii) biorefinery-driven microalgae plant, focused on the recovery of added-value bioproducts (zeaxanthin and phycocyanin) along with ethanol and CHP production. These main scenarios and several variants were modelled and optimized for a small-scale demo plant of 1000 Lethanol/day and extrapolated for larger production capacities. Results showed that despite the innovative approach of direct production of ethanol by microalgae, the bioenergy-driven scenario is non-feasible under the studied conditions. Conversely, ethanol production becomes economically feasible as co-product in the biorefinery-driven scenario although having payback periods>10 years. Furthermore, if only bio-based products are produced the NPV and the payback are even more positive, 104.8 M€ and ca. 5 years, respectively.info:eu-repo/semantics/publishedVersio

A Molybdenum(VI) Complex of 5-(2-pyridyl-1-oxide)tetrazole: synthesis, structure, and transformation into a MoO3-Based hybrid catalyst for the epoxidation of Bio-Olefins

The discovery of heterogeneous catalysts synthesized in easy, sustainable ways for the valorization of olefins derived from renewable biomass is attractive from environmental, sustainability, and economic viewpoints. Here, an organic–inorganic hybrid catalyst formulated as [MoO3 (Hpto)]·H2O (2), where Hpto = 5-(2-pyridyl-1-oxide)tetrazole, was prepared by a hydrolysis– condensation reaction of the complex [MoO2Cl2 (Hpto)]·THF (1). The characterization of 1 and 2 by FT-IR and Raman spectroscopies, as well as 13C solid-state NMR, suggests that the bidentate N,O-coordination of Hpto in 1 (forming a six-membered chelate ring, confirmed by X-ray crystallography) is maintained in 2, with the ligand coordinated to a molybdenum oxide substructure. Catalytic studies suggested that 2 is a rare case of a molybdenum oxide/organic hybrid that acts as a stable solid catalyst for olefin epoxidation with tert-butyl hydroperoxide. The catalyst was effective for converting biobased olefins, namely fatty acid methyl esters (methyl oleate, methyl linoleate, methyl linolenate, and methyl ricinoleate) and the terpene limonene, leading predominantly to the corresponding epoxide products with yields in the range of 85–100% after 24 h at 70 ◦C. The versatility of catalyst 2 was shown by its effectiveness for the oxidation of sulfides into sulfoxides and sulfones, at 35 ◦C (quantitative yield of sulfoxide plus sulfone, at 24 h; sulfone yields in the range of 77–86%). To the best of our knowledge, 2 is the first molybdenum catalyst reported for methyl linolenate epoxidation, and the first of the family [MoO3 (L)x] studied for methyl ricinoleate epoxidation.LA/P/0006/2020; POCI-01-0145-FEDER-030075; ALG-01-0145-FEDER-022121; grant ref. 2021.06403.BD; grant ref. 2021.04756.BD;info:eu-repo/semantics/publishedVersio

Biomedical potential of fucoidan, a seaweed sulfated polysaccharide: from a anticancer agent to a building block of cell encapsulating systems for regenerative medicine

Marine macroalgae or seaweeds synthesize a wide variety of polymers and smaller compounds with several bioactivities, among which the sulfated polysaccharides acquire greater relevance not only due to the reported antioxidant, antiviral and anticancer[1] activities, but also to the resemblance of extracellular matrix glycosaminoglycans found in the human body[2]. In this study, the potential of fucoidan (Fu) isolated from brown seaweed Fucus vesiculosus for therapeutical use has been evaluated, focusing in its performance as antitumoral agent (bioactive role) or as building block of cell encapsulating systems (structural role). Materials and Methods: The anticancer activity of Fu extracts was assessed by evaluating the cytotoxic behavior over two human breast cancer cell lines (MCF-7 and MDA-MB-231) in in-vitro culture, using human fibroblasts and endothelial cells (HPMEC-ST1 and MRC-5, respectively) as reference. Regarding the structural role, Fu was modified by methacrylation reaction (MFu) using methacrylic acid and further crosslinked using visible radiation and triethanolamine and eosin-y as photoinitiators. The photocrosslinking was performed on MFu solution droplets placed in a silica-based superhydrophobic surface[3], allowing the formation of particles[4] (since natural Fu is highly soluble in water and ion gelation is not effective). Biological performance of the developed particles was assessed by in vitro culture of fibroblasts and pancreatic cells (L929 and 1.1B4, respectively) in contact with MFu particles, up to 7 days. The ability of the developed materials to support adhesion and proliferation of cells was evaluated for both types of cells. Results and Discussion: The tested anticancer activity is not ubiquitous on Fu extracts, being dependent on its chemical features, with molecular weight (Mw) representing a particular role. Specifically, Mw values around 60 kDa exhibited cytotoxic effects to human breast cancer cell lines, while not affecting normal fibroblasts or endothelial cells (which represent the cells of the healthy tissue that would be closer to the tumor in a real situation). A concentration range of 0.2 to 0.3 mg mL-1 from the selected Fu extract could be considered as the therapeutic window for further studies. Regarding fucoidanâ s role on innovative biomaterials, the developed MFu particles could support the proliferation of fibroblasts (L929), but also of human pancreatic beta cells (1.1B4), which tend to form pseudo-islets after 7 days in culture (Fig. 1). This pancreatic cells could be also successfully encapsulated, opening a new route for a diabetes mellitus type 1 therapeutic approach. Fig. 1: Confocal microscopy images of 1.1B4 cells cultured in the presence of fucoidan-based particles and organized in pseudo-islets (red â actin; blue â nuclei). Conclusion: The present work establishes fucoidan as a high performance building block for the development of advanced therapies for cancer (targeted therapy) or tissue and organ regeneration. It shed light on the relation between chemical structure and biological activity towards anti-cancer effect and proposes novel beta cell laden particles as injectable insulin producing systems to tackle diabetes.Funding from projects 0687_NOVOMAR_1_P (co-funded by INTERREG 2007-2013 / POCTEP), CarbPol_u_Algae (EXPL/MAR-BIO/0165/2013, funded by the Portuguese Foundation for Science and Technology, FCT), POLARIS (FP7-REGPOT-CT2012-316331) and ComplexiTE (ERC-2012-ADG 20120216-321266), funded by the European Union’s Seventh Framework Programme for Research and Development is acknowledged. ASF, SSS, NMO and DSC are also thankful to FCT for their individual fellowships

Glycation potentiates α-synuclein-associated neurodegeneration in synucleinopathies

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Cognitive differentiation during childhood: A study on cognitive profiles of 5, 7, and 9-year-old children

No seio do debate sobre se a inteligência é mais bem definida por um fator geral ou por aptidões específicas, ganha relevância a hipótese da diferenciação cognitiva. Análises recentes enfatizam o interesse dessa questão para a investigação e alertam para a relevância das suas implicações na área educativa. Este estudo analisou a possibilidade de a diferenciação das aptidões cognitivas ocorrer já na infância e também o efeito moderador do Quociente de Inteligência na magnitude da relação entre as habilidades cognitivas. Aplicou-se uma bateria de provas que avaliam várias funções cognitivas a uma amostra de 231 crianças com 5, 7 e 9 anos, distribuídas por três grupos de desempenho cognitivo. Os resultados de uma análise de clusters hierárquica e de uma análise de variância apontam para a não diferenciação das funções cognitivas na infância. Contudo, uma análise mais cuidadosa aponta para alguma diferenciação suportada pela heterogeneidade dos perfis cognitivos junto dos alunos com Quociente de Inteligência elevado.Within the debate about whether intelligence is best defined by a general factor or specific skills, the hypothesis of cognitive differentiation gains relevance. Recent analyses have emphasized the importance of this issue in the investigation of cognitive skills and have highlighted its implications in education. This study examined the possibility that the differentiation of cognitive abilities may occur during childhood and investigated the moderating effect of Intelligence Quotient on the magnitude of the relationship between cognitive abilities. A battery of tests for assessing cognitive function was administered to 231 children aged 5, 7, and 9 years old, who were divided into three cognitive performance groups. The results of hierarchical cluster analysis and variance analysis indicate the lack of differentiation of cognitive functions during childhood. However, a more careful analysis suggests some differentiation supported by the heterogeneity of cognitive profiles among students with high Intelligence Quotient.FCT -Fundação para a Ciência e a Tecnologia(SFRH/BD/84153/2012