Synthesis, optical and electrical characterization of amino-alcohol based sol-gel hybrid materials

This manuscript describes the synthesis and characterization of five new organic–inorganic hybrid (OIH) sol-gel materials that were obtained from a functionalized siloxane 3-glycidoxypropyltrimethoxysilane (GPTMS) by the reaction with the new Jeffamine®, namely three different diamines, i.e., EDR-148, RFD-270, and THF-170, a secondary diamine, i.e., SD-2001, and a triamine, i.e., T-403. The OIH sol-gel materials were characterized by UV-visible absorption spectrophotometry, steady-state photoluminescence spectroscopy, and electrochemical impedance spectroscopy. The reported OIH sol-gel materials showed that, with the exception of the samples prepared with Jeffamine® SD-2001, the transmittance values ranged between 61% and 79%. Regarding the capacitance data, the values reported changed between 0.008 and 0.013 nF cm−2. Due to their optical and electrical properties these new OIH materials show promising properties for applications as support films in an optical sensor area such as fiber sensor devices. Studies to assess the chemical stability of the OIH materials in contact with cement pastes after 7, 14, and 28 days were also performed. The samples prepared with THF–170 and GPTMS, when compared to the samples prepared with RFD-270 and T-403, exhibited improved behavior in the cement paste (alkaline environment), showing promising properties for application as support film in optical fiber sensors in the civil engineering field.This research was funded by the “SolSensors—Development of Advanced Fiber Optic Sensors for Monitoring the Durability of Concrete Structures” project, with the Program Budget COMPETE—Operational Program Competitiveness and Internationalization—COMPETE 2020 reference and the Lisbon Regional Operational Program (its FEDER component)

Potential of an estuarine salt marsh plant (Phragmites australis (Cav.) Trin. Ex Steud10751) for phytoremediation of bezafibrate and paroxetine

This study aimed to evaluate the potential of a salt marsh plant and its rhizosphere microorganisms for the removal of two pharmaceutical compounds, bezafibrate and paroxetine, from estuarine environment. Plants were exposed for 7 days to a simplified estuarine medium, elutriate solution with or without sediment, doped with bezafibrate or paroxetine. Tests were done in absence and presence of nutrients or copper. Phragmites australis (Cav.) Trin. Ex Steud, alone or with the sediment microbial communities, contributed for pharmaceuticals removal. In the presence of P. australis, for paroxetine a 65% removal was observed. Removal increased up to 90% when sediment was present. For bezafibrate, removals reached ca. 47% in P. australis presence, increasing to ca. 70% when nutrients were added to the medium, indicating a good nutritional state can contribute for a higher compound removal. When Cu was added, 75% removal for bezafibrate and 95% removal for paroxetine were observed indicating the metal might influence the removal of the pharmaceuticals. Overall, the plant and its rhizosediments and associated microorganisms showed potential for pharmaceuticals removal from estuaries, eventually degrading the selected compounds, a feature requiring more research. Results indicate that phytoremediation could be a viable option for eliminating/diminishinginfo:eu-repo/semantics/publishedVersio

Sol-Gel Coating Membranes for Optical Fiber Sensors for Concrete Structures Monitoring

The use of advanced sensing devices for concrete and reinforced concrete structures (RCS) is considered a rational approach for the assessment of repair options and scheduling of inspection and maintenance strategies. The immediate benefits are cost reduction and a reliable prevention of unpredictable events. The use of optical fiber sensors (OFS) for such purposes has increased considerably in the last few years due to their intrinsic advantages. In most of the OFS, the chemical transducer consists of immobilized chemical reagents placed in the sensing region of the optical sensor by direct deposition or by encapsulation in a polymeric matrix. The choice of the support matrix impacts directly on the performance of the OFS. In the last two decades, the development of OFS functionalized with organic-inorganic hybrid (OIH) sol-gel membranes have been reported. Sol-gel route is considered a simple method that offers several advantages when compared to traditional synthesis processes, allowing to obtain versatile materials with unique chemical and physical properties, and is particularly valuable in the design of OIH materials. This review will provide an update of the current state-of-the-art of the OFS based on OIH sol-gel materials for concrete and RCS since 2016 until mid-2021. The main achievements in the synthesis of OIH membranes for deposition on OFS will be discussed. The challenges and future directions in this field will also be considered, as well as the main limitations of OFS for RCS monitoring. (c) 2021 by the authors. Licensee MDPI, Basel, Switzerland

Natural materials

The use of naturally occurring materials as scaffolds to support cell growth and proliferation significantly impacted the origin and progress of tissue engineering and regenerative medicine. However, the majority of these materials failed to provide adequate cues to guide cell differentiation toward the formation of new tissues. Over the past decade, a new generation of multifunctional and smart natural-based materials has been developed to provide biophysical and biochemical cues intended to specifically guide cell behavior. In this chapter, the use of extracellular matrix proteins and blood-derivatives intrinsic capacity to mimic the biophysical and biological characteristics of native tissues is reviewed. Furthermore, the design of a variety of nanostructures using the well-explored characteristics of nucleic acids is summarized. In the second section, the exploitation of supramolecular chemistry to create new dynamic functional hydrogels that mimic the extracellular matrix structure and/or composition is surveyed. Then, the incorporation of nanoelements in polymeric networks for the design of smart nanocomposite materials with tailored functionalities to guide cell behavior is introduced. Finally, the future perspectives in the development of new biomaterials for tissue engineering and regenerative medicine are presented.Te authors acknowledge the fnancial support of the European Union Framework Programme for Research and Innovation Horizon 2020, under the TEAMING grant agreement No 739572 – Te Discoveries CTR, Marie Skłodowska-Curie grant agreement No 706996 and European Research Council grant agreement No 726178; FCT (Fundação para a Ciência e a Tecnologia) and the Fundo Social Europeu através do Programa Operacional do Capital Humano (FSE/POCH) in the framework of Ph.D. grants PD/BD/113807/2015 (BBM) and PD/BD/129403/2017 (SMB), Post-Doc grant SFRH/ BPD/112459/2015 (RMD) and project SmarTendon (PTDC/NAN-MAT/30595/2017); Project NORTE01-0145-FEDER-000021 supported by Norte Portugal Regional Operational Programme (NORTE 2020), under the PORTUGAL 2020 Partnership Agreement, through the European Regional Development Fund (ERDF

Simultaneous Papillary Carcinoma in Thyroglossal Duct Cyst and Thyroid

Thyroglossal duct cyst (TDC) is a cystic expansion of a remnant of the thyroglossal duct tract. Carcinomas in the TDC are extremely rare and are usually an incidental finding after the Sistrunk procedure. In this report, an unusual case of a 36-year-old woman with concurrent papillary thyroid carcinoma arising in the TDC and on the thyroid gland is presented, followed by a discussion of the controversies surrounding the possible origins of a papillary carcinoma in the TDC, as well as the current management options

Hybrid sol-gel matrices doped with colorimetric/fluorimetric imidazole derivatives

Organic–inorganic hybrids (OIH) are materials that can be easily synthesized by the sol–gel method and combine the advantages of organic and inorganic moieties within a single polymeric matrix. Imidazole derivatives are versatile organic compounds that can change their optical properties with the variation of pH due to the protonation or deprotonation of the nitrogen atoms. This work reports the preparation of different OIHs doped with different contents of two imidazole compounds (3a,b). The obtained materials were characterized structurally by FTIR, and the dielectric properties were studied by electrochemical impedance spectroscopy. The optical properties were studied by UV-Vis absorption and fluorescence spectroscopies. The FTIR analysis showed that the presence of the imidazole does not change the structural properties of the matrices. The normalized resistance values obtained for the doped matrices ranged between 8.57 and 9.32 Ω cm2, all being higher than the undoped matrix. The σ ranged between 9.49 and 10.28 S cm−1, being all higher than the pure OIH samples. Compound 3a showed a maximum absorption peak at 390 nm, which is present in the OIH spectra, proving the presence of the compound. In the case of compound 3b, a maximum absorption wavelength at 412 nm was found, and the compound peak was not clear, which may indicate that an interaction between the compound and the matrix occurred. A synergetic effect between the intrinsic emission of the matrix and the fluorescence of 3a is found on the OIH-doped matrices.This research was funded by Fundação para a Ciência e Tecnologia (FCT) and FEDER (European Fund for Regional Development)-COMPETE-QRENEU through the Chemistry Research Centre of the University of Minho (Ref. CQ/UM (UID/QUI/00686/2019 and UID/QUI/00686/2020), project “SolSensors—Development of Advanced Fiber Optic Sensors for Monitoring the Durability of Concrete Structures”, reference POCI-01-0145-FEDER-031220, and a PhD grant to R.P.C.L. Sousa (SFRH/BD/145639/2019). The NMR spectrometer Bruker Avance III 400 is part of the National NMR Network (PTNMR) and partially supported by Infrastructure Project No 022161 (co-financed by FEDER through COMPETE 2020, POCI and PORL and FCT through PIDDAC)

Injectable and magnetic responsive hydrogels with bioinspired ordered structures

Injectable hydrogels are particularly interesting for applications in minimally invasive tissue engineering and regenerative medicine strategies. However, the typical isotropic microstructure of these biomaterials limits their potential for the regeneration of ordered tissues. In the present work, we decorated rod-shaped cellulose nanocrystals with magnetic nanoparticles and coated these with polydopamine and polyethylene glycol polymer brushes to obtain chemical and colloidal stable nanoparticles. Then, these nanoparticles (0.1-0.5 wt %) were incorporated within gelatin hydrogels, creating injectable and magnetically responsive materials with potential for various biomedical applications. Nanoparticle alignment within the hydrogel matrix was achieved under exposure to uniform low magnetic fields (108 mT), resulting in biomaterials with directional microstructure and anisotropic mechanical properties. The biological performance of these nanocomposite hydrogels was studied using adipose tissue derived human stem cells. Cells encapsulated in the nanocomposite hydrogels showed high rates of viability demonstrating that the nanocomposite biomaterials are not cytotoxic. Remarkably, the microstructural patterns stemming from nanoparticle alignment induced the directional growth of seeded and, to a lower extent, encapsulated cells in the hydrogels, suggesting that this injectable system might find application in both cellular and acellular strategies targeting the regeneration of anisotropic tissues.Fundação para a Ciência e a Tecnologia for SFRH/BPD/112459/2015 (RD), EU’s H2020 programme for Marie Skłodowska-Curie grant agreement 706996 and for European Research Council grant agreement 772817 - MagTendon, project RECOGNIZE (UTAPICDT/CTM-BIO/0023/2014), project FOOD4CELLS (PTDC/CTM-BIO/4706/2014 - POCI-01- 0145-FEDER 016716) (PB), and project NORTE-01-0145-FEDER-000021

Intrinsically bioactive cryogels based on platelet lysate nanocomposites for hemostasis applications.

The currently used hemostatic agents are highly effective in stopping hemorrhages but have a limited role in the modulation of the wound-healing environment. Herein, we propose an intrinsically bioactive hemostatic cryogel based on platelet lysate (PL) and aldehyde-functionalized cellulose nanocrystals (a-CNCs). PL has attracted great attention as an inexpensive milieu of therapeutically relevant proteins; however, its application as a hemostatic agent exhibits serious constraints (e.g., structural integrity and short shelf-life). The incorporation of a-CNCs reinforced the low-strength PL matrix by covalent cross-linking its amine groups that exhibit an elastic interconnected porous network after full cryogelation. Upon blood immersion, the PL-CNC cryogels absorbed higher volumes of blood at a faster rate than commercial hemostatic porcine gelatin sponges. Simultaneously, the cryogels released biomolecules that increased stem cell proliferation, metabolic activity, and migration as well as downregulated the expression of markers of the fibrinolytic process. In an in vivo liver defect model, PL-CNC cryogels showed similar hemostatic performance in comparison with gelatin sponges and normal material-induced tissue response upon subcutaneous implantation. Overall, owing to their structure and bioactive composition, the proposed PL-CNC cryogels provide an alternative off-the-shelf hemostatic and antibacterial biomaterial with the potential to deliver therapeutically relevant proteins in situ.The authors thank Hospital da Prelada (Porto, Portugal) for providing adipose tissue samples and Instituto Portugues do Sangue e Transplantacio-IPST (Portugal) (Porto, Portugal) for providing platelet concentrates. The authors would like to thank Alain Morais and Isabel Pires for their support in the in vivo procedure and histological evaluation, respectively. The authors would like to thank the anonymous reviewers for all useful and helpful comments on our manuscript. This work was supported by the European Research Council grant agreement no. 772817, FCT/MCTES (Fundacio para a Ciencia e a Tecnologia/Ministerio da Ciencia, Tecnologia, e Ensino Superior) and the Fundo Social Europeu atraves do Programa Operacional do Capital Humano (FSE/POCH) in the framework of Ph.D. grant PD/59/2013-PD/BD/113807/2015 (BBM) and CEECIND/01375/2017 (MGF), Norwegian Research Council for project no. 287953

Human-based nanocomposite cryogels for hemostatic and wound healing applications

In trauma surgery, a fast and effective hemostatic agent is crucial to prevent death. The current used hemostatic sponges are highly effective in stopping the hemorrhages, however they have a limited stability, shape memory, and biological functionality to induce an efficient regenerative healing after injury. Blood derivatives have attracted great attention as an inexpensive milieu of bioactive molecules (e.g., growth factors, cytokines), self-assembling scaffolding proteins (e.g., fibrinogen, fibronectin, vitronectin), and antimicrobial peptides (e.g., platelet factor-4) that have the ability to enhance angiogenesis, stem cell recruitment, and tissue regeneration. Among those, platelet lysate (PL) has attracted great attention as a milieu of supra-physiological doses of biomolecules that can be easily standardized. However, the current PL scaffolds showed limited stability and weak mechanical strength, which severely limits its performance as a bioinstructive and hemostatic biomaterial. Herein, we propose the use of aldehyde-functionalized CNC (a-CNC) that will be crosslinked through reversible Schiff base bonds established with the amine groups of PL proteins to produce a stable hemostatic cryogel for wound healing applications.EU’s H2020 programme for grant agreement 706996 and 739572 - The Discoveries CTR; FCT for SFRH/BPD/112459/2015, PD/BD/113807/2015, FOOD4CELLS (PTDC/CTM-BIO/4706/2014-POCI-01- 0145- FEDER 016716) and project NORTE-01-0145- FEDER-000021

Profiling of lung microbiota discloses differences in adenocarcinoma and squamous cell carcinoma

The lung is a complex ecosystem of host cells and microbes often disrupted in pathological conditions. Although bacteria have been hypothesized as agents of carcinogenesis, little is known about microbiota profile of the most prevalent cancer subtypes: adenocarcinoma (ADC) and squamous cell carcinoma (SCC). To characterize lung cancer (LC) microbiota a first a screening was performed through a pooled sequencing approach of 16S ribosomal RNA gene (V3-V6) using a total of 103 bronchoalveaolar lavage fluid samples. Then, identified taxa were used to inspect 1009 cases from The Cancer Genome Atlas and to annotate tumor unmapped RNAseq reads. Microbial diversity was analyzed per cancer subtype, history of cigarette smoking and airflow obstruction, among other clinical data. We show that LC microbiota is enriched in Proteobacteria and more diverse in SCC than ADC, particularly in males and heavier smokers. High frequencies of Proteobacteria were found to discriminate a major cluster, further subdivided into well-defined communities’ associated with either ADC or SCC. Here, a SCC subcluster differing from other cases by a worse survival was correlated with several Enterobacteriaceae. Overall, this study provides first evidence for a correlation between lung microbiota and cancer subtype and for its influence on patient life expectancy.We would like to thank all patients for donating their samples and for collaborating in this study. IPATIMUP integrates the i3S Research Unit, which is partially supported by the Portuguese Foundation for Science and Technology (FCT). This work was supported by the Portuguese Foundation for Science and Technology (FCT), financed by the European Social Funds (COMPETE-FEDER) and National Funds through the FCT (projects PEstC/SAU/LA0003/2013 and POCI-01-0145-FEDER-007274, fellowships SFRH/BPD/77646/2011 and SFRH/BPD/120777/2016 to S.G. and P.I.M., respectively, grant PTDC/BEXGMG/0242/2012 to S.S. and by Programa Operacional Regional do Norte (ON.2 – O Novo Norte and Norte 2020), through FEDER funds under the Quadro de Referência Estratégico Nacional (QREN; projects NORTE-07-0162-FEDER-00018 and NORTE-070162-FEDER-000067, and NORTE-01-0145-FEDER-000029)