Assessment of ciprofloxacin photocatalysis by-products toxicity with Vibrio fischeri

The presence of pharmaceuticals in water has become a large concern due to the potential negative effects on humans and aquatic ecosystems. From these pharmaceuticals, antibiotics represent a serious problem since their overuse and misuse may lead to adverse environmental effects, in particular, toxicity to microflora and fauna and potential negative effects to humans [1]. Photocatalysis has become attractive to promote the degradation of contaminants in the aquatic environment since it allows their rapid and efficient removal from water, transforming them into by-products [2]. In order to evaluate toxicity of these by-products, several bio tests using bacteria (Vibrio fischeri) and algae (Daphnia spp.), among others, have been used [3]. In the present work a photocatalytic systems using commercial TiO2 and ZnO nanoparticles in suspension was used to degrade ciprofloxacin under UV radiation. Samples were withdraw over time in order to monitor degradation and toxicity. The luminescence of the bacteria Vibrio fischeri was used to test the toxicity of ciprofloxacin intermediate compounds, produced during the photocatalysis process. If a substance is toxic towards these bacteria, their normal luminescence decreases, as a consequence of a decreasing bacteria viability. Results (Figure 1) indicate that samples without ciprofloxacin degradation (t=0), in contact with bacteria (for 35 min), result in a higher luminescence than with completely degraded ciprofloxacin (t=15min). These results indicate that by products are responsible for low bacteria viability.FEDER through the COMPETE Program and by the Portuguese Foundation for Science and Technology (FCT) in the framework of the Strategic Project PEST-C/FIS/UI607/2011 and project PTDC/CTM-NAN/121038/2010

Environmental impact of nanomaterials: assessment of toxicity in chemical and biological processes for the degradation of micropollutants.

This study was supported by FCT under the scope of the strategic funding of UID/BIO/04469/2013 unit and COMPETE 2020 (POCI-01-0145-FEDER-006684) and BioTecNorte operation (NORTE-01-0145-FEDER-000004) funded by the European Regional Development Fund under the scope of Norte2020 - Programa Operacional Regional do Norteinfo:eu-repo/semantics/publishedVersio

Effect of temperature on the oxidation of soybean biodiesel

This paper proposes to examine the effect of temperature on the oxidation behavior of biodiesel. Soybean biodiesel was oxidized at different temperatures (room temperature, 60, and 110 °C), and the increase in primary and secondary oxidation products was determined based on the peroxide and anisidine values, respectively, during the induction period (IP). The results indicated that the evolution of hydroperoxides followed zero-order reaction kinetics during the IP at all temperatures, and their rate of formation was exponentially affected by temperature. It was also deduced that temperature influenced the ratio between primary and secondary oxidation products formation, which decreased as the temperature increased. Additionally, it was possible to predict the oxidation behavior of the soybean biodiesel at room temperature by an exponential model fitted to the IP values at different temperatures (70, 80, 90, 100, and 110 °C) using the Rancimat apparatus.The authors are grateful to the São Paulo Research Foundation (FAPESP) for their financial support and to the Coordination for the Improvement of Higher Level or Education Personnel (CAPES) for a scholarship (Process n° BEX 6667/12-0).Peer Reviewe

The effect of nanotube surface oxidation in the electrical response of MWCNT/PVDF nanocomposites

Carbon nanotubes / poly(vinylidene fluoride) composites were prepared using CNT with different oxidation and thermal treatments. The oxidation procedure leads to CNT with the most acidic characteristics that lower the degree of crystallinity of the polymer and contribute to a large increase of the dielectric constant. The surface treatments, in general, increase percolation threshold and decrease conductivity, but, on the other hand, are able to promote the nucleation of the electroactive phase of the polymer, which is suitable for the use of PVDF in sensors, actuators and other smart materials applications. Finally, the surface treatments do not seem to affect CNT interaction among them, reaching similar degrees of dispersion in all cases, as shown by the SEM results. The maximum value of the dielectric constant is ~630. It is demonstrated that the composite conductivity can be attributed to a hopping mechanism that is strongly affected by the surface treatment of the CNT.The authors thank the Fundacao para a Ciencia e a Tecnologia (FCT), Portugal, for financial support through the projects PTDC/CTM/69316/2006 and NANO/NMed-SD/0156/2007), and CIENCIA 2007 program for S.A.C.; V. S., J.S. and J.N.P. also thank FCT for the SFRH/BPD/63148/2009, SFRH/BD/60623/2009 and SFRH/BD/66930/2009 grants

Designing antimicrobial biomembranes via clustering amino-modified cellulose nanocrystals on silk fibroin β-sheets

The continuous rising of infections caused by multidrug-resistant pathogens is becoming a global healthcare concern. Developing new bio-based materials with unique chemical and structural features that allow efficient interaction with bacteria is thus important for fighting this phenomenon. To address this issue, we report an antimicrobial biomaterial that results from clustering local facial amphiphilicity from amino-modified cellulose on silk fibroin β-sheets, by simply blending the two components through casting technology. A simple but effective method for creating a membrane that is antibacterial and non-cytotoxic. Amino-modified cellulose nanocrystals (CNC-NH2) were mixed with proteinaceous silk fibroin (SF) which resulted in a material with improved crystallinity, higher β-sheet content, and exposed amino-groups at its surface features, proven by Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS), that does not occur when the components are individually assembled. The resulting material possesses important antibacterial activity inducing >3 CFU log10 reduction of Escherichia coli and Staphylococcus epidermidis, while the pristine membranes show no antibacterial effect. The chemical interactions occurring between SF and CNC-NH2 during casting, exposing the amino moieties at the surface of the material, are proposed as the main reason for this antimicrobial activity. Importantly, the membranes are non-cytotoxic, showing their potential to be used as a new bioinspired material with intrinsic antibacterial activity for biomedical applications. Those may include coatings for medical devices for the control of healthcare-associated infections, with no need for including external antimicrobial agents in the material.This work has been supported by FCT – Fundação para a Ciência e a Tecnologia (FCT) under the scope of the strategic funding of UID/FIS/04650/2020, project PTDC/BTM-MAT/28237/2017 and grants SFRH/BD/145455/2019 (EOC), SFRH/BD/140698/2018 (RBP) and SFRH/BPD/121464/2016 (MMF). The authors also acknowledge funding by Spanish State Research Agency (AEI) and the European Regional Development Fund (ERFD) through the project PID2019-106099RB-C43/AEI/10.13039/501100011033 and from the Basque Government Industry Department under the ELKARTEK program. Finally, the authors thank for the technical and human support provided by SGIker of UPV/EHU

An unusual artefact in the late prehistoric of the iberian northwest: the rock milling equipment

Los equipos de molienda rupestres (EMR) son un tipo de artefactos que en ocasiones ha sido identificado como un motivo más dentro del Arte Rupestre Atlántico (ARA), que apenas ha recibido atención en la investigación. A diferencia de los molinos de vaivén tradicionales éstos tienen la particularidad de estar realizados sobre superficies rocosas, lo que les confiere un carácter eminentemente fijo, compartiendo - en ocasiones - soporte con arte rupestre. Los datos actuales disponibles definen un ámbito de distribución geográfica muy específica y localizada en el entorno sur de las Rías Baixas gallegas. El objetivo de este este trabajo es hacer una síntesis actualizada del conocimiento y una primera sistematización de estos artefactos, así como una búsqueda de paralelos arqueológicos y/o etnográficos. Los datos publicados en la actualidad indican la escasez de artefactos de molienda y/o triturado de materiales sobre soportes rocosos fijos en el continente europeo, probablemente por falta de investigación. Ahora bien, existen diversos paralelos en otras regiones del globo, que evidencian la complejidad funcional y cultural de este tipo de elementos.Rock milling equipment (EMR) is an artifact that has sometimes been identified as a motif of Atlantic Rock Art (ARA), but has received few attentions by researchers. Unlike traditional mills, these have the particularity of being made on outcropping surfaces, which gives them an eminently fixed feature, and share – sometimes - support with rock art. The current available data define a specific and localised geographical range in the south of the Galician Rías Baixas. This work is aimed at performing an updated synthesis of knowledge and a first systematization of these artifacts, as well as a find for archaeological and/or ethnographic parallels. Currently published data displays a shortage of milling and/or grinding artifacts on fixed rock supports on the European continent, probably due to low research intensity. However, there are several parallels in other regions of the globe, which highlight the functional and cultural complexity of these artefacts.Ministerio de Economía y Competitividad | Ref. HAR2012-34029Xunta de Galicia | Ref. ED481B-2018/06

TiO2/graphene and TiO2/graphene oxide nanocomposites for photocatalytic applications: A computer modeling and experimental study

Supplementary data related to this article can be found at http://dx. doi.org/10.1016/j.compositesb.2018.03.015.This work reports a computational study, focused on graphene (G) and graphene oxide (GO) interfaces with titanium dioxide (TiO2), and an experimental assay on the photocatalytic activity of TiO2/G and TiO2/GO nanocomposites in the degradation of two different pollutants: methylene blue and ciprofloxacin. Both carbon nanostructures were compared due to their different chemical structure: GO is a G derivative with oxygen functional groups which should promote a closer chemical interaction with TiO2 nanoparticles. Computational models of the fundamental properties of the composites indicated potentially improved photocatalytic activity compared to TiO2, namely lower band gaps and charge carrier segregation at the interfaces. These fundamental properties match qualitatively experimental results on methylene blue, which was more effectively degraded by TiO2/G and TiO2/GO nanocomposites than by pure TiO2 under UV light. In contrast, the same nanocomposites were found to be less efficient to degrade ciprofloxacin than pure TiO2 under visible and UV light. Therefore, this work showcases the relevance of an efficient matching between the catalyst and the molecular properties and structure of the pollutant.This work was supported by the Portuguese Foundation for Science and Technology (FCT) in the framework of the Strategic Project PESTC/FIS/UI607/2014 and PEST-C/QUI/UIO686/2014 and the CICECO Aveiro Institute of Materials, POCI-01-0145-FEDER-007679 (FCT ref. UID/CTM/50011/2013). Access to computing facilities provided by the Project “Search-ON2: Revitalization of HPC infrastructure of UMinho” (NORTE-07-0162-FEDER-000086) is also acknowledged. P. M. Martins and Luciana Pereira thanks the FCT for grants SFRH/BD/98616/2013 and SFRH/BPD/110235/2015, respectively. MMF for a program Ciência 2008 fellowship. The authors thank financial support from the Basque Government Industry Department under the ELKARTEK Program. P.A.A.P. Marques thanks the grant IF/00917/2013/CP1162/ CT0016. Acknowledges also to FCT under the scope of the strategic funding of UID/BIO/04469/2013 unit and COMPETE 2020 (POCI-010145-FEDER-006684) and BioTecNorte operation (NORTE-01-0145FEDER-000004) funded by the European Regional Development Fund under the scope of Norte2020 - Programa Operacional Regional do Norte.info:eu-repo/semantics/publishedVersio

Photocatalytic activity of TiO2/graphene and TiO2/graphene oxide nanocomposites

Semiconductor-based heterogeneous photocatalysis has been one of the most promising processes for the treatment of contaminated water. Among the available catalysts, titanium dioxide (TiO2) presents the best photocatalytic properties, being chemically and biologically inert, stable, non-toxic, cheap and easy to produce. However, its energy bang gap lies in the ultraviolet (UV) range, which is responsible for a reduced spectral activation, since UV radiation corresponds to only 5% of the solar spectrum [1]. For this reason, one of the main purposes of the scientific community has been to improve the photocatalytic performance of TiO2, namely through an adequate doping of this material, or through the creation of nanocomposites, to enable photocatalysis occurrence by the incidence of visible light. One alternative concerns the application of nanocomposites of TiO2 with graphene and graphene oxide to photocatalytic processes [2]. In this work, nanocomposites of TiO2 with different weight concentrations of graphene and graphene oxide (namely 0.5%, 1%, 1.5% and 3%) were synthetized by a one-step hydrothermal method and characterized in terms of morphology, crystalline structure, vibrational modes and optical band gap. The photocatalytic activity of these nanocomposites was then evaluated through the degradation of methylene blue and ciprofloxacin solutions under UV and visible radiation. The results indicated that the studied nanocomposites presented higher degradation rates of the methylene blue than the pure TiO2, which increased with the content of graphene/graphene oxide. However, these composites proved to be less suitable to degrade the ciprofloxacin solution than the pure TiO2 nanoparticles.Portuguese Foundation for Science and Technology (FCT) - UID/FIS/04650/2013, PTDC/CTM-ENE/5387/2014 and SFRH/BD/98616/2013; Basque Government Industry Department under the ELKARTEK Program.info:eu-repo/semantics/publishedVersio

Sustainable Collagen Composites with Graphene Oxide for Bending Resistive Sensing

This work reports on the development of collagen films with graphene oxide nanoparticles (GO NPs), aiming toward the development of a new generation of functional sustainable sensors. For this purpose, different GO NP contents up to 3 wt % were incorporated into a collagen matrix, and morphological, thermal, mechanical and electrical properties were evaluated. Independently of the GO NP content, all films display an increase in thermal stability as a result of the increase in the structural order of collagen, as revealed by XRD analysis. Further, the inclusion of GO NPs into collagen promotes an increase in the intensity of oxygen characteristic absorption bands in FTIR spectra, due to the abundant oxygen-containing functional groups, which lead to an increase in the hydrophilic character of the surface. GO NPs also influence the mechanical properties of the composites, increasing the tensile strength from 33.2 ± 2.4 MPa (collagen) to 44.1 ± 1.0 MPa (collagen with 3 wt % GO NPs). Finally, the electrical conductivity also increases slightly with GO NP content, allowing the development of resistive bending sensors.This research was funded by Grant PID2021-124294OB-C22 funded by MCI/AEI10.13039/501100011033 and by “ERDF A way of making Europe”. This work was also supported by the Basque Government (IT1658-22) and the Portuguese Foundation for Science and Technology (FCT) under strategic funding UIDB/04650/2020, UID/FIS/04650/2021, project PTDC/FIS-MAC/28157/2017, and Investigator FCT Contract 2020.02915.CEECIND (D.M.C) and 2020.04028.CEECIND (C.M.C.) funded by national funds through FCT and by the ERDF through the COMPETE2020-Programa Operacional Competitividade e Internacionalização (POCI). The authors also acknowledge funding from the Basque Government Industry and Education Department under the ELKARTEK program. M.A. thanks the Basque Government for her fellowship (POS_2022_1_0007)

Enhanced photocatalytic activity of Au/TiO2 nanoparticles against ciprofloxacin

In the last decades, photocatalysis has arisen as a solution to degrade emerging pollutants such as antibiotics. However, the reduced photoactivation of TiO2 under visible radiation constitutes a major drawback because 95% of sunlight radiation is not being used in this process. Thus, it is critical to modify TiO2 nanoparticles to improve the ability to absorb visible radiation from sunlight. This work reports on the synthesis of TiO2 nanoparticles decorated with gold (Au) nanoparticles by deposition-precipitation method for enhanced photocatalytic activity. The produced nanocomposites absorb 40% to 55% more radiation in the visible range than pristine TiO2, the best results being obtained for the synthesis performed at 25 °C and with Au loading of 0.05 to 0.1 wt. %. Experimental tests yielded a higher photocatalytic degradation of 91% and 49% of ciprofloxacin (5 mg/L) under UV and visible radiation, correspondingly. Computational modeling supports the experimental results, showing the ability of Au to bind TiO2 anatase surfaces, the relevant role of Au transferring electrons, and the high affinity of ciprofloxacin to both Au and TiO2 surfaces. Hence, the present work represents a reliable approach to produce efficient photocatalytic materials and an overall contribution in the development of high-performance Au/TiO2 photocatalytic nanostructures through the optimization of the synthesis parameters, photocatalytic conditions, and computational modeling.This work was supported by the Portuguese Foundation for Science and Technology (FCT) in the framework of the strategic projects UID/FIS/04650/2013 by Fundo Europeu de Desenvolvimento Regional (FEDER) funds through the COMPETE 2020—Programa Operacional Competitividade e Internacionalização (POCI) with the reference project POCI-01-0145-FEDER-006941, project PTDC/CTM-ENE/5387/2014, as well as UID/BIO/04469 unit through COMPETE 2020 (POCI-01-0145-FEDER-006684) and BioTecNorte operation (NORTE-01-0145-FEDER-000004) funded by the European Regional Development Fund under the scope of Norte2020—Programa Operacional Regional do Norte. P.M. Martins thanks the FCT for the grant SFRH/BD/98616/2013 and Luciana Pereira for the grant SFRH/BPD/110235/2015. M. Melle-Franco would like to acknowledge support from Centro de Investigação em Materiais Cerâmicos e Compósitos (CICECO)—Aveiro Institute of Materials, POCI-01-0145-FEDER007679 (UID/CTM/50011/2013) and the FCT (IF/00894/2015).info:eu-repo/semantics/publishedVersio