Publications

Abstract Phenol red (X-PR) and malachite green carbinol (MGC) are two textile finishing dyes, which are present in aquatic environments through industrial effluents. Due to the toxic nature of both dyes, they are harmful to human health. In the present study, two materials, barley seeds and the biochar of barley (Hordeum vulgare L.), were used to remove the dyes in an aqueous solution. The materials used are characterized by AFM, FTIR, SEM, XRD and EDX techniques. In this study, the parameters studied are the adsorbent dose, pH, initial adsorbate concentration and contact time. The maximum equilibrium time was found to be 90 min for all dyes. Kinetic studies revealed that the adsorption of X-PR and MGC on barley seeds (BS-HVL) and the biochar of barley (BC-HVL) followed pseudo-second-order kinetics and that both porous and intraparticle diffusion mechanisms were involved. The adsorption equilibrium data were well fitted to the Langmuir and Freundlich isotherm model for both materials, and the maximum adsorption capacity of monolayer and multilayers for X-PR and MGC were 71.642 mg g(-1) and 50 mg g(-1) on BS-HVL, and 44.843 mg g(-1) and 121.95 mg g(-1) on BC-HVL, respectively. The thermodynamic results reveal that the dye removal on barley was endothermic and spontaneous in nature.

Abstract <jats:p>Brown carbon is a type of carbonaceous aerosol with strong light absorption in the ultraviolet and visible wavelengths that leads to radiative forcing. However, it is difficult to correlate the chemical composition of brown carbon with its atmospheric light absorption properties, which translates into significant uncertainty. Thus, a time-dependent density functional theory (TD-DFT) approach was used to model the real-world absorption properties of 14 polycyclic aromatic hydrocarbons (PAHs) over three regions of the Basque Country (Spain): Bilbao, Urretxu, and Azpeitia. The data were corrected for atmospheric concentration. The results show that the absorption spectra over each region are qualitatively identical, with the absorption intensities being significantly higher over Bilbao than over Azpeitia and Urretxu. Furthermore, it was found that the light absorption by PAHs should be more relevant for radiative forcing when it occurs at UVA and (sub)visible wavelengths. Finally, among the 14 studied PAHs, benzo[b]fluoranthene, pyrene, fluoranthene, benzo[a]pyrene, and benzo[k]fluoranthene and benzoperylene were identified as the molecules with larger contributions to radiative forcing.</jats:p>

Abstract In this work, TiO2-based nanomaterials have been successfully synthesized by doping TiO2 with Co, Mn, and Ni and by co-doping it with (P,Mo) or (P,W). The structural, optical, and morphological properties of the synthesized nanomaterials have been investigated using various techniques such as XRD, FTIR spectroscopy, UV-vis diffuse reflectance spectroscopy, XPS, and SEM-EDS. The obtained results showed that the crystalline structure of the doped TiO2-based nanomaterials depends strongly on the nature of the doping ions. The obtained band gap energy of TiO2 co-doped with (P,Mo) changes to a level below the band gap energy of TiO2 anatase indicating a high ability to absorb visible light. The obtained photocatalytic activity results of methyl orange degradation showed that, under visible light, the mono-doping of TiO2 with Co and its co-doping with (P,Mo) or (P,W) improve significantly the photocatalytic activity of TiO2 in comparison with undoped TiO2. The activity order obtained under UV-A irradiation for the used photocatalysts is TiO2 > > 1%Ni-TiO2 > 1%Co-TiO2 > 30%(P,Mo)-TiO2 approximate to 30%(P,W)TiO2 > 1%Mn-TiO2 while under visible light, it is 1%Co-TiO2 > 30%(P,Mo)-TiO2 > 30%(P,W)TiO2 approximate to TiO2 > 1%Ni-TiO2 > 1%Mn-TiO2. The high photocatalytic activity observed for these samples could be the result of a synergetic effect of the high visible light absorption capacity and the low recombination rate of photoexcited electrons and holes.

Abstract <jats:p>In the environmental, industrial, and biomedical fields, pH monitorization is of the upmost importance. However, the most used type of pH sensors, glass pH-electrodes, still present limitations in their application in low volume samples and in cellular pH sensing, due to their size and invasive nature. Fluorescence-based sensors present a solution to such issues, providing a non-invasive solution to pH sensing. Herein, we report the rational development of carbon dots (CDs) as a pH nanosensor via an active surface preservation (ASP) method. Carbon dots (CDs) are carbon-based fluorescent nanoparticles with valuable properties such as high aqueous solubility, low cost and good biocompatibility, with remarkable fluorescence performance, been increasingly used as fluorescent nanosensors. Namely, these nanomaterials present advantages over molecular probes in terms of (photo)stability and water solubility, among others. By employing ASP strategies, the CDs will be prepared by using precursors with known active functional features. The ASP method allows the nanoparticles to retain the structural features of precursors, thus retaining their properties, without the need for costly and time-consuming post-synthesis functionalization procedures. In this work, we intend to provide a proof-of-concept of this type of strategy by utilizing the known pH-sensitivity of fluorescein to provide a pH-based response to CDs. The resulting CDs presented reversible response by fluorescence enhancement in the range of pH from 4 to 12. The nanoparticles exhibited excellent photostability, in different pH solutions. The studied CDs were also unaffected by, either variation of ionic strength or the presence of interferent species, while being compatible with human cancer cells. Finally, CDs were able to determine the pH of real samples. Thus, a selective pH fluorescent CDs-based nanosensor was developed.</jats:p>

Abstract Parkinson & rsquo;s Disease (PD) is a neurodegenerative disorder affecting more than 10 million people worldwide. Currently, PD has no cure and no early diagnostics methods exist. Mitochondrial dysfunction is presented in the early stages of PD, and it is considered an important pathophysiology component. We have previously developed mitochondria-targeted hydroxycinnamic acid derivatives, presenting antioxidant and iron-chelating properties, and preventing oxidative stress in several biological models of disease. We have also demonstrated that skin fibroblasts from male sporadic PD patients (sPD) presented cellular and mitochondrial alterations, including increased oxidative stress, hyperpolarized and elongated mitochondria and decreased respiration and ATP levels. We also showed that forcing mitochondrial oxidative phosphorylation (OXPHOS) in sPD fibroblasts uncovers metabolic defects that were otherwise hidden. In this work, we tested the hypothesis that a lead mitochondriatargeted hydroxycinnamic acid derivative would revert the phenotype found in skin fibroblasts from sPD patients. Our results demonstrated that treating human skin fibroblasts from sPD patients with non-toxic concentrations of AntiOxCIN4 restored mitochondrial membrane potential and mitochondrial fission, decreased autophagic flux, and enhanced cellular responses to stress by improving the cellular redox state and decreasing reactive oxygen species (ROS) levels. Besides, fibroblasts from sPD patients treated with AntiOxCIN4 showed increased maximal respiration and metabolic activity, converting sPD fibroblasts physiologically more similar to their sex- and agematched healthy controls. The positive compound effect was reinforced using a supervised machine learning model, confirming that AntiOxCIN4 treatment converted treated fibroblasts from sPD patients closer to the phenotype of control fibroblasts. Our data points out a possible mechanism of AntiOxCIN4 action contributing to a deeper understanding of how the use of mitochondria-targeted antioxidants based on a polyphenol scaffold can be used as potential drug candidates for delaying PD progression, validating the use of fibroblasts from sPD patients with more active OXPHOS as platforms for mitochondria-based drug development.

Abstract Water quality management will be a priority issue in the near future. Indeed, due to scarcity and/or contamination of the water, regulatory frameworks will be increasingly strict to reduce environmental impacts of wastewater and to allow water to be reused. Moreover, drinking water quality standards must be improved in order to account for the emerging pollutants that are being detected in tap water. These tasks can only be achieved if new improved and sustainable water treatment technologies are developed. Nanomaterials are improving the ongoing research on advanced oxidation processes (AOPs). This work reviews the most important AOPs, namely: persulfate, chlorine and NH2Cl based processes, UV/H2O2, Fenton processes, ozone, and heterogeneous photocatalytic processes. A critical review of the current coupling of nanomaterials to some of these AOPs is presented. Besides the active role of the nanomaterials in the degradation of water contaminants/pollutants in the AOPs, the relevance of their adsorbent/absorbent function in these processes is also discussed.

Abstract Carbon dots (CDs) are carbon-based nanomaterials with advantageous luminescent properties, making them promising alternatives to other molecular and nanosized fluorophores. However, the development of CDs is impaired by the low synthesis yield of standard fabrication strategies, making high-yield strategies essential. To help future studies to focus on cleaner production strategies, we have employed a Life Cycle Assessment (LCA) to compare and understand the environmental impacts of available routes for the high-yield synthesis of carbon dots. These routes were: (1) production of hydrochar, via hydrothermal treatment of carbon precursors, and its alkaline-peroxide treatment into high-yield carbon dots; (2) thermal treatment of carbon precursors mixed in a eutectic mixture of salts. Results show that the first synthesis route is associated with the lowest environmental impacts. This is attributed to the absence of the mixture of salts in the first synthesis route, which offsets its higher electricity consumption. Sensitivity analysis showed that the most critical parameter in the different synthetic strategies is the identity of the carbon precursor, with electricity being also relevant for the first synthesis route. Nevertheless, the use of some carbon precursors (as citric acid) with higher associated environmental impacts may be justified by their beneficial role in increasing the luminescent performance of carbon dots. Thus, the first synthesis route is indicated to be the most environmental benign and should be used as a basis in future studies aimed to the cleaner and high-yield production of carbon dots.

Abstract Dioxetanone is one of the prototypical cyclic peroxide intermediates in several chemiluminescent and bioluminescent systems, in which thermolysis reactions allow efficient singlet chemiexcitation. While the chemiexcitation mechanism of dioxetanone and peroxide intermediates is still far from understood, the presence of a peroxide bond that undergoes bond breaking has been found to be a constant. Here we have addressed the following questions: can other non-peroxide bonds lead to chemiexcitation and, if not, can the differences between dioxetanone and non-peroxide derivatives help to elucidate their chemiexcitation mechanism? To this end, we have used a reliable TD-DFT approach to model the thermolysis and chemiexcitation of a model dioxetanone and its three other non-peroxide derivatives. The results showed that only the dioxetanone molecule could lead to chemiluminescence as it is the only one for which thermolysis is energetically favorable and provides a pathway for singlet chemiexcitation. Finally, the chemiexcitation of the model dioxetanone is explained by its access, during thermolysis, to a biradical region where the ground and excited states are degenerate. This occurs due to an increased interaction between the reaction fragments, which extends the biradical regions and delays the rupture of the peroxide ring.

Abstract <jats:p>The present work reports an experimental thermodynamic study of two nitrogen heterocyclic organic compounds, fenclorim and clopyralid, that have been used as herbicides. The sublimation vapor pressures of fenclorim (4,6-dichloro-2-phenylpyrimidine) and of clopyralid (3,6-dichloro-2-pyridinecarboxylic acid) were measured, at different temperatures, using a Knudsen mass-loss effusion technique. The vapor pressures of both crystalline and liquid (including supercooled liquid) phases of fenclorim were also determined using a static method based on capacitance diaphragm manometers. The experimental results enabled accurate determination of the standard molar enthalpies, entropies and Gibbs energies of sublimation for both compounds and of vaporization for fenclorim, allowing a phase diagram representation of the (p,T) results, in the neighborhood of the triple point of this compound. The temperatures and molar enthalpies of fusion of the two compounds studied were determined using differential scanning calorimetry. The standard isobaric molar heat capacities of the two crystalline compounds were determined at 298.15 K, using drop calorimetry. The gas phase thermodynamic properties of the two compounds were estimated through ab initio calculations, at the G3(MP2)//B3LYP level, and their thermodynamic stability was evaluated in the gaseous and crystalline phases, considering the calculated values of the standard Gibbs energies of formation, at 298.15 K.</jats:p>

Abstract The aim of the present study was to investigate the eco-cytotoxicity of several forms of nanomaterials (NM), such as nano-CuO, nano-TiO2, nano-SiO2 and nano-ZnO, on different aquatic species (Raphidocelis subcapitata, Daphnia magna and Lemna minor) following standard protocols and on human cell lines (Caco-2, SV-80, HepG2 and HaCaT). Predicted no-effect concentrations (PNEC) or hazard concentrations for 5% of the species (HC5) were also estimated based on the compilation of data available in the literature. Most of the NM agglomerated strongly in the selected culture media. For the ecotoxicity assays, nano-CuO and nano-ZnO even in particle agglomeration state were the most toxic NM to the freshwater organisms compared to nano-TiO2 and nano-SiO2. Nano-ZnO was the most toxic NM to R. subcapitata and D. magna, while nano-CuO was found to be very toxic to L. minor. Nano-CuO was very toxic to Caco-2 and HepG2 cells, particularly at the highest tested concentrations, while the other NM showed no toxicity to the different cell lines. The HC5 and PNEC values are still highly protective, due to data limitations. However, the present study provides consistent evidence of the potential risks of both nano-CuO and nano-ZnO against aquatic organisms and also their effects on public health.