Chemical constituents of Euphorbia hyberna L. (Euphorbiaceae)

Chemical investigation of the aerial part and the roots of Euphorbia hyberna L. subs. hyberna. resulted in the isolation and identification of four triterpenoids (3�-O-octadecanoyllupeol (1), glut-5-en-3�-ol (2), 24-methylenecicloartan-3�-ol (3) and cicloart-23-ene-3�,25-diol (6)) along with the phenolic compounds ellagic acid (4) and 3,30 -di-O-methylellagic acid (7). Although these are all known compounds, this is the first report of their isolation from this plant. Their structures were elucidated on the basis of spectral methods, including 2D NMR experiences, and confirmed by comparing with the literature data.info:eu-repo/semantics/publishedVersio

Photochromic properties of thienylpyrrole azo dyes in solution

The photochromic behaviour of thienylpyrrole azo dyes in THF solutions was studied for the first time. The photochromic properties are strongly dependent on the substitution pattern on the dyes. Nitro-substituted thienylpyrrole azo dyes are particularly interesting since they exhibit very fast colouration/decolouration processes. The activation energies of these compounds are among the lowest values reported for heterocyclic azo dyes. These compounds show aggregation phenomena in freshly prepared solutions of THF, which lead to variable photochromic behaviours. Only after 1–5 h the solutions reach equilibrium and then reproducible photochromic behaviour can be observed.Fundação para a Ciência e Tecnologia (FCT

Novel photochromic 2,2´-bithiophene azo dyes

The photochromic behaviour of two series of 2,2’-bithiophene azo dyes in THF solutions was studied. The photochromic properties and colour constancy were strongly dependent on the substitution pattern of the dyes. Under visible irradiation (> 420 nm) while some dyes exhibited a significant change in the colour intensity others exhibited an almost stable absorption. The photokinetic parameters of these systems are described.Fundação para a Ciência e a Tecnologia (FCT

Ab initio modeling of defects in silicon, germanium and SiGe alloys

Understanding the most elemental defects in semiconductors is a fundamental step to grasp the countless solid-state reactions that may occur during crystal growth, device processing and operation stages. The higher carrier mobilitity in SiGe alloys and germanium, when compared with silicon, and the necessity to a higher K dielectric than SiO2 makes these semiconductors the most contendors to a new generation of electronic devices. Our aim is to model self and impurity point defects in SiGe alloys and germanium, and compare with their equivalent complexes in silicon. We use density functional theory and pseudopotentials to determine the structural, electronic and vibrational properties. The calculations are performed in a 32 CPU PC cluster, in Physics Department of Aveiro University.Fundação para a Ciência e a Tecnologia (FCT).INTAS

Characterization of decavanadate and decaniobate solutions by Raman spectroscopy

The decaniobate ion, (Nb10 = [Nb10O28]6−) being isoelectronic and isostructural with the decavanadate ion (V10 = [V10O28]6−), but chemically and electrochemically more inert, has been useful in advancing the understanding of V10 toxicology and pharmacological activities. In the present study, the solution chemistry of Nb10 and V10 between pH 4 and 12 is studied by Raman spectroscopy. The Raman spectra of V10 show that this vanadate species dominates up to pH 6.45 whereas it remains detectable until pH 8.59, which is an important range for biochemistry. Similarly, Nb10 is present between pH 5.49 and 9.90 and this species remains detectable in solution up to pH 10.80. V10 dissociates at most pH values into smaller tetrahedral vanadate oligomers such as V1 and V2, whereas Nb10 dissociates into Nb6 under mildly (10 > pH > 7.6) or highly alkaline conditions. Solutions of V10 and Nb10 are both kinetically stable under basic pH conditions for at least two weeks and at moderate temperature. The Raman method provides a means of establishing speciation in the difficult niobate system and these findings have important consequences for toxicology activities and pharmacological applications of vanadate and niobate polyoxometalates

Decavanadate, decaniobate, tungstate and molybdate interactions with sarcoplasmic reticulum Ca2+-ATPase: quercetin prevents cysteine oxidation by vanadate but does not reverse ATPase inhibition

Recently we demonstrated that the decavanadate (V10) ion is a stronger Ca2+-ATPase inhibitor than other oxometalates, such as the isoelectronic and isostructural decaniobate ion, and the tungstate and molybdate monomer ions, and that it binds to this protein with a 1 : 1 stoichiometry. The V10 interaction is not affected by any of the protein conformations that occur during the process of calcium translocation (i.e. E1, E1P, E2 and E2P) (Fraqueza et al., J. Inorg. Biochem., 2012). In the present study, we further explore this subject, and we can now show that the decaniobate ion, [Nb10 = Nb10O28]6−, is a useful tool in deducing the interaction and the non-competitive Ca2+-ATPase inhibition by the decavanadate ion [V10 = V10O28]6−. Moreover, decavanadate and vanadate induce protein cysteine oxidation whereas no effects were detected for the decaniobate, tungstate or molybdate ions. The presence of the antioxidant quercetin prevents cysteine oxidation, but not ATPase inhibition, by vanadate or decavanadate. Definitive V(IV) EPR spectra were observed for decavanadate in the presence of sarcoplasmic reticulum Ca2+- ATPase, indicating a vanadate reduction at some stage of the protein interaction. Raman spectroscopy clearly shows that the protein conformation changes that are induced by V10, Nb10 and vanadate are different from the ones induced by molybdate and tungstate monomer ions. Here, Mo and W cause changes similar to those by phosphate, yielding changes similar to the E1P protein conformation. The putative reduction of vanadium(V) to vanadium(IV) and the non-competitive binding of the V10 and Nb10 decametalates may explain the differences in the Raman spectra compared to those seen in the presence of molybdate or tungstate. Putting it all together, we suggest that the ability of V10 to inhibit the Ca2+- ATPase may be at least in part due to the process of vanadate reduction and associated protein cysteine oxidation. These results contribute to the understanding and application of these families of mono- and polyoxometalates as effective modulators of many biological processes, particularly those associated with calcium homeostasis.MA thanks CCMAR; LAEBC and MPMM thank QFM-UC for financial support. CAO is grateful for a QEII fellowship and Discovery Project grant (DP110105530) from the Australian Research Council. WHC acknowledges support from the U.S. Department of Energy Office of Basic Energy Science via grant DE-FG02-05ER15693, the National Science Foundation via EAR-0814242 and an NSF CCI grant through the Center for Sustainable Materials Chemistry, number CHE-1102637

Design and Optimization of Microbial Fuel Cells and Evaluation of a New Air-Breathing Cathode Based on Carbon Felt Modified with a Hydrogel—Ion Jelly®

Funding Information: This research was funded by Fundação para a Ciência e a Tecnologia projects DSAIPA/DS/0117/2020, UIDB/04565/2020, and UIDP/04565/2020, by the Associate Laboratory Institute for Health and Bioeconomy—i4HB project LA/P/0140/2020. This work was supported by the Associate Laboratory for Green Chemistry—LAQV financed by national funds from FCT/MCTES (UIDB/50006/2020). We also thank Fundação para a Ciência e Tecnologia (FCT) for funding (SFRH/BD/77568/2011 (R.N.L.C.); SFRH/BPD/80293/2011 (R.M.A.)). C.M.C. acknowledges FCT for the Ciência 2008 Program; S.V.R. acknowledges the financial support from FCT (Portuguese Foundation for Science and Technology) for a postdoctoral research grant (FRH/BPD/33864/2009). This work was supported by the Associate Laboratory for Green Chemistry—LAQV, financed by national funds from FCT/MCTES (UIDB/50006/2020 and UIDP/50006/2020); the Institute for Bioengineering and Biosciences—iBB, financed by FCT (UID/BIO/04565/2013); and from Programa Operacional Regional de Lisboa 2020 (Project N. 007317). Publisher Copyright: © 2023 by the authors.The increased demand for alternative sustainable energy sources has boosted research in the field of fuel cells (FC). Among these, microbial fuel cells (MFC), based on microbial anodes and different types of cathodes, have been the subject of renewed interest due to their ability to simultaneously perform wastewater treatment and bioelectricity generation. Several different MFCs have been proposed in this work using different conditions and configurations, namely cathode materials, membranes, external resistances, and microbial composition, among other factors. This work reports the design and optimization of MFC performance and evaluates a hydrogel (Ion Jelly®) modified air-breathing cathode, with and without an immobilized laccase enzyme. This MFC configuration was also compared with other MFC configuration performances, namely abiotic and biocathodes, concerning wastewater treatment and electricity generation. Similar efficiencies in COD reduction, voltage (375 mV), PD (48 mW/m2), CD (130 mA/m2), and OCP (534 mV) were obtained. The results point out the important role of Ion Jelly® in improving the MFC air-breathing cathode performance as it has the advantage that its electroconductivity properties can be designed before modifying the cathode electrodes. The biofilm on MFC anodic electrodes presented a lower microbial diversity than the wastewater treatment effluent used as inocula, and inclusively Geobacteracea was also identified due to the high microbial selective niches constituted by MFC systems.publishersversionpublishe

Methodology for phytoplankton taxonomic group identification towards the development of a lab-on-a-chip

This paper presents the absorbance and fluorescence optical properties of various phytoplankton species, looking to achieve an accurate method to detect and identify a number of phytoplankton taxonomic groups. The methodology to select the excitation and detection wavelengths that results in superior identification of phytoplankton is reported. The macroscopic analyses and the implemented methodology are the base for designing a lab-on-a-chip device for a phytoplankton group identification, based on cell analysis with multi-wavelength lighting excitation, aiming for a cheap and portable platform. With such methodology in a lab-on-a-chip device, the analysis of the phytoplankton cells’ optical properties, e.g., fluorescence, diffraction, absorption and reflection, will be possible. This device will offer, in the future, a platform for continuous, autonomous and in situ underwater measurements, in opposition to the conventional methodology. A proof-of-concept device with LED light excitation at 450 nm and a detection photodiode at 680 nm was fabricated. This device was able to quantify the concentration of the phytoplankton chlorophyll a. A lock-in amplifier electronic circuit was developed and integrated in a portable and low-cost sensor, featuring continuous, autonomous and in situ underwater measurements. This device has a detection limit of 0.01 µ/L of chlorophyll a, in a range up to 300 µg/L, with a linear voltage output with chlorophyll concentration.Fundação para a Ciência e a Tecnologia | Ref. UIDB/04436/2020Fundação para a Ciência e a Tecnologia | Ref. UIDP/04436/2020Fundação para a Ciência e a Tecnologia | Ref. PD/BD/150581/2020Fundação para a Ciência e a Tecnologia | Ref. 2021.01087.CEECINDFundação para a Ciência e a Tecnologia | Ref. 2021.01086.CEECIN

Methodology for phytoplankton taxonomic group identification towards the development of a lab-on-a-chip

This paper presents the absorbance and fluorescence optical properties of various phytoplankton species, looking to achieve an accurate method to detect and identify a number of phytoplankton taxonomic groups. The methodology to select the excitation and detection wavelengths that results in superior identification of phytoplankton is reported. The macroscopic analyses and the implemented methodology are the base for designing a lab-on-a-chip device for a phytoplankton group identification, based on cell analysis with multi-wavelength lighting excitation, aiming for a cheap and portable platform. With such methodology in a lab-on-a-chip device, the analysis of the phytoplankton cells’ optical properties, e.g., fluorescence, diffraction, absorption and reflection, will be possible. This device will offer, in the future, a platform for continuous, autonomous and in situ underwater measurements, in opposition to the conventional methodology. A proof-of-concept device with LED light excitation at 450 nm and a detection photodiode at 680 nm was fabricated. This device was able to quantify the concentration of the phytoplankton chlorophyll a. A lock-in amplifier electronic circuit was developed and integrated in a portable and low-cost sensor, featuring continuous, autonomous and in situ underwater measurements. This device has a detection limit of 0.01 µ/L of chlorophyll a, in a range up to 300 µg/L, with a linear voltage output with chlorophyll concentration.European Regional Development Fund (ERDF) through the Interreg VA Spain-Portugal (POCTEP) 2014–2020 Program under grant agreement 0591_FOODSENS_1_E, under the national support to R&D units grant, through the reference project UIDB/04436/2020 and UIDP/04436/2020, and by project NORTE-08-5369-FSE-000039 co-founded by the European Social Fund FSE and through National funds NORTE 2020 and Regional Operacional Programa of North 2014/2020. The University of Vigo work was funded by a Xunta de Galicia grant to the Biological Oceanography Research Group (Consolidación e estruturación de unidades). This output reflects only the views of the authors, and the program authorities cannot be held responsible for any use that may be made of the information contained therei

Tuning the Biological Activity of Camphorimine Complexes through Metal Selection

This research was funded by FCT—Fundação para a Ciência e a Tecnologia, through projects CQE (UIDB/00100/2020 and UIDP/00100/2020) and C2TN (UID/MULTI/04349/2019), the projects of the Research Unit Institute for Bioengineering and Biosciences—iBB (UIDB/04565/2020 and UIDP/04565/2020), the project LA/P/0140/2020 of the Associate Laboratory Institute for Health and Bioeconomy—i4HB, and a PhD grant to J.P.C. (UI/BD/152244/2021).The cytotoxic activity of four sets of camphorimine complexes based on the Cu(I), Cu(II), Ag(I), and Au(I) metal sites were assessed against the cisplatin-sensitive A2780 and OVCAR3 ovarian cancer cells. The results showed that the gold complexes were ca. one order of magnitude more active than the silver complexes, which in turn were ca. one order of magnitude more active than the copper complexes. An important finding was that the cytotoxic activity of the Ag(I) and Au(I) camphorimine complexes was higher than that of cisplatin. Another relevant aspect was that the camphorimine complexes did not interact significantly with DNA, in contrast with cisplatin. The cytotoxic activity of the camphorimine complexes displayed a direct relationship with the cellular uptake by OVCAR3 cells, as ascertained by PIXE (particle-induced X-ray emission). The levels of ROS (reactive oxygen species) formation exhibited an inverse relationship with the reduction potentials for the complexes with the same metal, as assessed by cyclic voltammetry. In order to gain insight into the toxicity of the complexes, their cytotoxicity toward nontumoral cells (HDF and V79 fibroblasts) was evaluated. The in vivo cytotoxicity of complex 5 using the nematode Caenorhabditis elegans was also assessed. The silver camphorimine complexes displayed the highest selectivity coefficients (activity vs. toxicity).publishersversionpublishe