Publications

Abstract <jats:p>The production of useful chemicals by electroreducing CO2 it is a promising approach to reduce the levels of this greenhouse gas in the atmosphere. This is not a straightforward process due to the high stability of the CO2 molecule and low selectivity however, these barriers can be overcome by using an appropriate catalyst. This research focus on the effect of pre-treating the carbon supports before incorporating the catalyst on the electroreduction of CO2. We found that the electrochemical behaviour of the carbon supports is modified by the nature of the pre-treatment used. From the structure perspective, the results showed partial destruction of the carbon structure mainly after the oxidative treatments nevertheless, the introduction of defect sites in the carbon structure contributed to catalyst performance. This improvement was proved by the LSV data that showed the reduction of the current associated with the hydrogen reduction reaction.</jats:p>

Abstract Diclofenac (DCF) is a very common pharmaceutical that, due to its high use and low removal rate, is considered a prominent contaminant in surface and groundwater worldwide. In this study, Solanum lycopersicum L. cv. MicroTom (tomato) was used to disclose the role of glutathione (GSH)-related enzymes, as GSH conjugation with DCF is a well reported detoxification mechanism in mammals and some plant species. To achieve this, S. lycopersicum plants were exposed to 0.5 and 5 mg L-1 of DCF for 5 weeks under a semi-hydroponic experiment. The results here obtained point towards an efficient DCF detoxification mechanism that prevents DCF bioaccumulation in fruits, minimizing any concerns for human health. Although a systemic response seems to be present in response to DCF, the current data also shows that its detoxification is mostly a root-specific process. Furthermore, it appears that GSH-mediated DCF detoxification is the main mechanism activated, as glutathione-S-transferase (GST) activity was greatly enhanced in roots of tomato plants treated with 5 mgL(-1) DCF, accompanied by increased glutathione reductase activity, responsible for GSH regeneration. By applying a targeted gene expression analysis, we provide evidence, for the first time, that SlGSTF4 and SlGSTF5 genes, coding for GSTs from phi class, were the main players driving the conjugation of this contaminant. In this sense, and even though tomato plants appear to be somewhat tolerant to DCF exposure, research on GST activity can prove to be instrumental in remediating DCF-contaminated environments and improving plant growth under such conditions.

Abstract Photocatalysis has received special attention from researchers that focus on evaluating its potential applications in the fields of energy, environment, and therapeutics, in an economically sustainable way. The photocatalysts that are most often discussed in literature are the ones composed of semiconductors, such as TiO2, ZnO, CdS, ZnS, CeO2 and WO3, since they possess an exquisite combination of optical, physical and chemical properties. Among these semiconductors, TiO2 has been amply studied due to its high refraction index, bandgap of 3.0-3.2 eV, high chemical and photostability, low cost and high range of potential applications. Within this scope, the obtainment of hollow spherical structures of micro- and nanometer size has been heavily motivated by an array of advantages such as high surface area, low density, high charge capacity, high shell permeability, amongst others. When compared to their bulk counterparts, literature data indicates a significant increase in photonic efficiency by using hollow spheres, mostly due to multiple processes of diffraction and reflection of light. Moreover, selectivity is an important feature of photocatalysts, that also enhances photonic efficiency. It may be expressed in two different manners. The first one concerns with selective photocatalysts to the substrate, which focus on the required surficial phenomena of adsorption of a target molecule by the photocatalyst before the catalysis reaction can take place. The second one concerns the selective photocatalysts to the desired product. In this review, the developments accomplished in recent years (mostly 2018 onwards) are addressed, encompassing a quite productive period, both regarding selectivity, hollowness and their synergisms. Product selectivity has been relying mainly on the utilization of metallic dopants, mostly noble metals. However, doping with non-metallic elements (N, F, P) and pairs of metallic elements, such as Pd/Cu and Au/Ag, appears to be gaining an increased acceptance. New insights into the mechanisms of selectivity by doping, besides the usual consideration of the reduction of band gap, were produced. A great vitality could also be found in the usage of cocatalysts (metal, metal/polymer, graphene). Concerning substrate selectivity, morphology and surface structuring have been the approaches of choice since a long time already. A recent trend was also identified, namely that of seeking synergisms between increasing photonic efficiency and increasing selective capacity, although this has presented itself as a challenge. An additional trend recently observed was that of attempting a simultaneous substrate and product selectivity, in order to make the photocatalytic process even more effective. In the case of hollow TiO2, this review addresses the control of crystallinity of the shell which is frequently under the risk of bursting due to the harsh conditions applied. To circumvent the possibility of bursting, two main strategies have been proposed, "silica-protected calcination" and "acid pretreatment". Finally, the combination of hollowness and selectivity has captured the attention of researchers. Molecular imprinting took the lead when it came to structuring the hollow shell, mostly via the post-calcination deposition of an imprinted polymer. To introduce product selectivity, modifications both of the outer and of the inner surface of the shell were reported. The possibility of tuning the properties of the outer and inner surfaces separately, opens new creative avenues in the field of TiO2-supported photocatalysis, with subsequent modification of reaction mechanisms.

Abstract <jats:p>This work introduces a method specially developed to produce a biorecognition element based on modified Stöber silica nanoparticles by the covalent immobilization of the human IgG. The sensing structure is based on long period fiber gratings (LPFG), specially developed to allow the interaction of the electromagnetic wave with the target analytes through its evanescent field. The surface was modified by the immobilization of the IgG-modified nanoparticles serving has recognition elements for specific target molecules. The resulting configuration was tested in the presence of anti-human IgG, recording the refractometric response of the modified LPFG in contact with different amounts of analyte. The selectivity of the sensor was also assessed.</jats:p>

Abstract The complex nature of electrode charge screening is well-known for ionic liquids (ILs). Due to strong ionion correlations, these electrolytes form a distinctive layered structure at interfaces. Variations in electrode potential cause structural changes that are reflected in a peculiar shape of differential capacitance-potential dependence with characteristic peaks. Although the differential capacitance for various ILs in conjunction with metal electrodes accessed via molecular dynamics (MD) simulations has been reported in the literature, retrieving a capacitance-potential curve, C(U), from the MD trajectories is not a trivial task. In this work, we present the results of the MD simulations of the IL 1-butyl-3-methylimidazolium hexafluorophosphate at a single-crystalline Au (100) surface. The discussion focuses on the simulation data treatment for C(U) curve fitting. It is shown that the resulting C strongly depends on the fitting method used. Four capacitance peaks and three structural reorganization types were identified in the studied system. With the help of a semi-quantitative approach in the framework of the original bilayer model of electric double layer (EDL), it is argued that the ions' reorientation is in the origin of the capacitance peaks. Also, it is shown that under the conditions of this study, the multilayer structure, characteristic of EDL in ILs on the whole, is far from the "lattice saturation" regime. The multilayer structure possesses a steric packing effect that impedes structural changes, decreasing the capacitance.

Abstract Deep eutectic solvents (DES) are often regarded as greener sustainable alternative solvents and are currently employed in many industrial applications on a large scale. Bearing in mind the industrial importance of DES-and because the vast majority of DES has yet to be synthesized-the development of cheminformatic models and tools efficiently profiling their density becomes essential. In this work, after rigorous validation, quantitative structure-property relationship (QSPR) models were proposed for use in estimating the density of a wide variety of DES. These models were based on a modelling dataset previously employed for constructing thermodynamic models for the same endpoint. The best QSPR models were robust and sound, performing well on an external validation set (set up with recently reported experimental density data of DES). Furthermore, the results revealed structural features that could play crucial roles in ruling DES density. Then, intelligent consensus prediction was employed to develop a consensus model with improved predictive accuracy. All models were derived using publicly available tools to facilitate easy reproducibility of the proposed methodology. Future work may involve setting up reliable, interpretable cheminformatic models for other thermodynamic properties of DES and guiding the design of these solvents for applications.</p>

Abstract This study aims to design and characterize Nanostructured lipid carriers (NLC) and Nanostructured lipid carrier-based hydrogels with Passiflora edulis seeds oil, a by-product from Madeira Island food industry. NLC were prepared by the ultrasonication technique, using passion fruit seeds oil as a liquid lipid and glyceryl distearate as a solid lipid. These NLC were then gelled with Poly (acrylic acid). Long-term stability studies were conducted with NLC and NLC-based hydrogels stored for 12 months. The following tests were performed: morphology, encapsulation efficiency, particle size analysis, polydispersity index analysis, zeta potential, pH measurement, color analysis, viscosity studies, texture analysis, in vitro occlusion test, ex vivo skin penetration study, tyrosinase inhibition activity, in vitro skin permeation experiments and in vitro cytotoxicity studies. The developed NLC had spherical shape and narrow particle sizes distribution with mean sizes in the range of 150 nm and PDI below 0.3, Zeta potential values around -30 mV and high Encapsulation efficiency. The tyrosinase inhibitory activity and skin retention of the nanoparticles was superior to that of the non-encapsulated oil. The developed formulations did not show cytotoxicity towards HaCat cells and presented suitable viscosity and texture properties for skin application, proving to be good candidates as depigmenting agent.

Abstract Determination of antibiotics in environmental waters is an important global issue. Although furazolidone (FZD) was banned from use in food-producing animals, owing to its mutagenic and carcinogenic effects, this antibiotic has been illegally used across the world and its presence in environment have being noted. In this work, the first selective molecularly imprinted polymer (MIP) was developed for electrochemical detection of FZD. It was constructed based on the modification of the traditional carbon paste electrode (CPE) with MIP microparticles, followed by introduction of multi-walled carbon nanotubes (MWCNTs). Quantum mechanical (QM) calculations and molecular dynamics (MD) simulations were performed to allow rational selection of an appropriate functional monomer and to simulate the best pre-polymerisation conditions, respectively. The MIP were synthetized by polymerization using 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) as monomer and FZD as template molecule. The MIP microparticles were then incorporated on CPE-MWCNTs and the electrochemical analysis of FZD were evaluated by differential pulse voltammetry (DPV). After optimisation of experimental conditions, the MIP-CPE-MWCNTs sensor exhibited a good linear response over the concentration range of 0.01 mu M to 1 mu M with a correlation coefficient of 0.9995. The limit of detection (LOD) was found to be 0.03 mu M (S/N = 3). Due to high imprinting efficiency the sensor displayed selectivity to recognise FZD molecules and it was successfully applied in water samples where excellent recovery values (over 90 %) were obtained. The proposed sensor provides an efficient and promising sustainable strategy for monitorisation of FZD in environmental waters.

Abstract The applicability of deep eutectic solvents is determined by their physicochemical properties. In turn, the properties of eutectic mixtures are the result of the components' molar ratio and chemical composition. Owing to the relatively low viscosities displayed by alcohol-based deep eutectic solvents (DESs), their application in industry is more appealing. Modeling the composition-property relationships established in polyalcohol-based mixtures is crucial for both understanding and predicting their behavior. In this work, a physicochemical property-structure comparison study is made between four choline chloride polyalcohol-based DESs, namely, ethaline, propeline, propaneline, and glyceline. Physicochemical properties obtained from molecular dynamic simulations are compared to experimental data, whenever possible. The simulations cover the temperature range from 298.15 to 348.15 K. The simulated and literature experimental data are generally in good agreement for all the studied DESs. Structural properties, such as radial and spatial distribution functions, coordination numbers, hydrogen bond donor (HBD)-HBD aggregate formation, and hydrogen bonding are analyzed in detail. The higher prevalence of HBD:HBD and HBD:anion hydrogen bonds is likely to be the major reason for the relatively high density and viscosity of glyceline as well as for lower DES self-diffusions.

Abstract Amitriptyline (AMT) frequent presence in environmental waters reflects the continuous consumption growth and raises issues on the importance of its monitorization. In this work, a sensitive and selective electrochemiluminescence (ECL) sensor was constructed using molecularly imprinted polymer (MIP) recognition element for AMT detection. Molecular dynamics (MD) simulations were performed to select the best functional monomer. Precipitation polymerization was followed to prepare the MIP micro spheres using methacrylic acid (MAA) as functional monomer, ethylene glycol methacrylate (EGDMA) as crosslinker and chloroform (CHL) as solvent. The MIP sensor was then prepared on a low cost and disposable screen-printed electrodes (SPCEs), previously modified with single-walled carbon nanotubes (SWCNTs), by drop coating a solution containing the MIP microspheres synthesized. The mechanism of detection was based in the system Ru(bpy)(3)(2+)/AMT, where AMT acts as co-reactor of Ru(bpy)(3)(2+) ECL. Several parameters controlling the preparation process of the sensor and AMT detection were optimised. The MIP/SWCNTs/SPCE ECL sensor showed good analytical performance with a linear correlation between ECL signal and the AMT concentration ranging from 0.1 to 200 mu M (R-2 = 0.9991). The limits of detection (LOD) and quantification (LOQ) were found to be 0.4 mu M (S/N = 3) and 1.5 mu M (S/N = 10), respectively. The MIP ECL sensor displayed good selectivity to recognise AMT molecules when compared with analoge structures and it was successfully applied in real water samples with good recovery values (90 to 112%). The developed MIP ECL sensor is suitable for integration with portable devices for AMT detection in environmental waters.