Publications

Abstract Soybean is a legume with high technological functionality, commonly used by the food industry as an ingredient in different products. However, soybean is an allergenic food whose undeclared presence in processed foods may represent a public health risk. In this work, it was developed an efficient electrochemical immunosensor, targeting the soybean trypsin inhibitor (Gly m TI) allergen using commercial anti-Gly m TI IgG, aiming at detecting/quantifying minute amounts of soybean in different food formulations. For this purpose, model mixtures of different foods (sausages, cooked-hams, biscuits) were prepared to contain known amounts of soybean protein isolate (100,000-0.1 mg kg(-1)) and submitted to specific thermal treatments (autoclaving, oven-cooking, baking). The electrochemical immunosensor allowed quantifying down to 0.1 mg kg(-1) of soybean in the three food matrices, raw and processed (0.0012 mg of Gly m TI/kg of matrix). Accordingly, the immunosensor is suitable for detecting traces of soybean in raw, processed, and complex foods, thus protecting 99 % of soybean-allergic patients.

Abstract Biomass-derived carbon dots (CDs) are gaining much interest in recent times, as they provide a sustainable option with abundant availability, a low cost and tunable luminescence. Herein, we report a simple green synthesis method to produce highly fluorescent CDs from Eucalyptus globulus leaves using the one-pot hydrothermal approach. The fabricated CDs exhibit strong blue fluorescence with an excitation and emission maxima of 320 nm and 445 nm, respectively. The highest quantum yield (QY) obtained was 60.7%. With the reported optical properties and biocompatibility, CDs can be looked at as a promising candidate for potential biosensing applications. Moreover, we employed a life cycle assessment (LCA) cradle-to-gate approach to study the environmental impacts of the synthesis strategy used for the fabrication of CDs. The results point out that citric acid is the main hotspot in CD synthesis, regarding environmental impacts in most categories. This justifies the introduction of biomass, which reduces the amount of citric acid, thus leading to a more sustainable synthesis strategy for fabricating CDs.

Abstract Carbon materials are readily available and are essential in energy storage. One of the routes used to enhance their surface area and activity is the decoration of carbons with semiconductors, such as amorphous TiO2, for application in energy storage devices.

Abstract Purpose Pejao Mining Complex locates in Castelo de Paiva municipality and, until its closure in 1994, was one of the most important coal mines in the Douro Coalfield. This work aims to study the presence, quantify, and evaluate the dissemination of mercury (Hg), a potentially toxic element (PTE) of major public health concern by the World Health Organization (WHO), from a waste pile affected by coal fires.Materials and methods Samples from areas affected and unaffected by the combustion and from surrounding soil were collected from Fojo waste pile region. First, the Hg pseudo-total concentration was estimated for all collected samples by soil microwave-assisted digestion with aqua regia (USEPA 3051A). Then, a sequential extraction procedure (SEP), the USEPA 3200, was applied for Hg fractionation and speciation aiming to evaluate Hg mobility and bioavailability to surrounding ecosystems.Results and discussion The results obtained showed a Hg enrichment in soil samples when compared to Portuguese and international reference values for soils. Relatively to the Hg availability and mobility, although it predominates in the semi-mobile fraction, the waste pile materials exposed to combustion showed a concerning increase of Hg levels in the mobile fraction that contains the more labile Hg species, being a major source of environmental contamination by Hg.Conclusions This study allowed to conclude that combustion of mining residues increased Hg mobility, toxicity, and bioavailability, increasing the contamination potential of the coal waste pile. The methodology applied in this work can be replicated in other abandoned mines to monitor, control, and/or mitigate the Hg environmental impact in the surrounding soils and waters.

Abstract Lithium-sulfur batteries are a promising alternative to lithium-ion batteries as they can potentially offer significantly increased capacities and energy densities. The ever-increasing global battery market demonstrates that there will be an ongoing demand for cost effective battery electrode materials. Materials derived from waste products can simultaneously address two of the greatest challenges of today, i.e., waste management and the requirement to develop sustainable materials. In this study, we detail the carbonisation of gelatin from blue shark and chitin from prawns, both of which are currently considered as waste biproducts of the seafood industry. The chemical and physical properties of the resulting carbons are compared through a correlation of results from structural characterisation techniques, including electron imaging, X-ray diffraction, Raman spectroscopy and nitrogen gas adsorption. We investigated the application of the resulting carbons as sulfur-hosting electrode materials for use in lithium-sulfur batteries. Through comprehensive electrochemical characterisation, we demonstrate that value added porous carbons, derived from marine waste are promising electrode materials for lithium-sulfur batteries. Both samples demonstrated impressive capacity retention when galvanostatically cycled at a rate of C/5 for 500 cycles. This study highlights the importance of looking towards waste products as sustainable feeds for battery material production.

Abstract Carbon electrodes, especially the glassy carbon electrodes (GCE) are widely accepted as very versatile sensing platforms. However, correlating the behaviour of the ferri/ferrocyanide redox couple ([Fe(CN) 6 ] 3-/4 ) with the GCE ' s surface modification is challenging. The surface modification can be achieved by applying a preconditioning electrochemical activation procedure. Hence, we report the investigation performed in order to provide further insights into the electrochemical behaviour of the commonly used redox probe in aqueous solutions. To that aim we took advantage of powerful and complementary electrochemical analytical techniques, like cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Thus, this work highlights the critical role of the GCE initial conditions for optimizing the charge transfer processes and therefore to improve the [Fe(CN) 6 ] 3-/4- performance in sensing applications. The best results were obtained in phosphate buffer saline solution with previous electrochemical activation by fast potential cycling between [-0.5 and +1.8] V (vs. Ag| AgCl (KCl sat.)). Finally, one can consider this an eco-friendly and simple procedure to be carried out in the lab, however, its use must be carefully optimized when exploring other systems, as highlighted herein.

Abstract The field of electrochemistry at the interface between two immiscible electrolyte solutions (ITIES) has been continuously expanding over the years due to their vast number of applications, including to investigate the partitioning of ionizable drugs at liquid-liquid systems. The aim of this Review is to highlight the great potential of ITIES as simple model of biological membranes to gather information on drug partition, lipophilicity, and pharmacokinetics that can be very useful for researchers in the field of drug discovery for development of new drugs with enhanced permeability. Relevant contributions and perspectives to improve the applicability of ITIES in partition studies were highlighted and discussed. The second part of this Review pretends to highlight the application of electrochemistry at the ITIES as experimental technique to investigate interactions between small ligands, including drugs, and DNA, a topic of high research interest in pharmaceutical and biological sciences, which remains with lots of opportunities to explore. Voltammetry at Liquid-Liquid Interfaces can be a versatile tool in the field of Drug Discovery as simple model for mimicking drug permeation through biological membranes helping to understand the partition of ionizable drugs between the aqueous and organic phases while providing fundamental information on its lipophilicity that can contribute to the design of new drugs with improved biological activity. image

Abstract Molecularly imprinted polymers (MIPs) are biomimetic materials of great interest in the scientific and industrial fields for the development of innovative sensing strategies. Herein, we proposed a new sensing application by developing an electrochemical sensor using molecular imprinting (MI) technology for recognition of atrial natriuretic peptide (ANP) both as a free molecule in solution and attached to nanoparticle-based drug delivery systems (DDSs), aiming to provide fast and reliable information on the cell uptake of nanoparticles (NPs). As proof of concept, poly(lactic-co-glycolic acid) (PLGA) NPs were synthesized and used as nanocarriers for ischemic heart disease therapy were synthesized and then functionalized with ANP (named here as PLGANPs@ANP). The MIP receptor film was prepared by electrochemical polymerization of dopamine over the working area of a gold screen-printed electrode (AuSPE), using cyclic voltammetry (CV) technique. The construction of the ANP sensor was carefully optimized to enhance its performance, including the film thickness and the procedures for effective template extraction from the MIP matrix. The MIP biosensor presented a linear response against polymeric NPs (PLGA-NPs@ANP) concentration logarithm ranging from 4.0 mu g mL(-1) to 100 mu g mL(-1), with a sensitivity of - 0.0129 mA mL mu g(-1) decade(-1) and an LOD < 4.0 g mL(-1). Furthermore, the developed MIP receptor film was able to discriminate ANP-functionalized nanocarriers from non-functionalized NPs.

Abstract Soil contamination with metals is a major threat for the environment and public health since most metals are toxic to humans and to non-human biota, even at low concentrations. Thus, new sustainable remediation approaches are currently needed to immobilize metals in soils to decrease their mobility and bioavailability. In this work, we explore the application of discarded substrates from hydroponic cultivation, namely coconut shell and a mixture of coconut shell and pine bark, for immobilization of metals (Cd, Cr, Ni, Cu, Pb, Hg, Sb and As) in a naturally contaminated soil from a mining region in Portugal. The immobilization capacity of substrates (added to the soil at 5% mass ratio) was assessed both individually and also combined with other traditional agriculture soil additives (limestone and gypsum, at 2% mass ratio) and nanoparticles of zero-valent iron (nZVI) at 1–3% mass ratio. The overall results obtained after a 30-d incubation showed that the discarded substrates are a viable, economic, and environmental-friendly solution for metal remediation in soils, with the capacity of immobilization ranging from 20 to 91% for the metals and metalloids studied. Furthermore, they showed the capacity to reduce the soil toxicity (EC50 ∼ 6000 mg/L) to non-toxic levels (EC50 > 10000 mg/L) to the bacteria Aliivrio fischeri. © 2024 The Authors

Abstract Over the last decades, the interface between two immiscible electrolyte solutions (ITIES) attracted considerable attention of the scientific community due to their vast applications, such as extraction, catalysis, partition studies and sensing. The aim of this Review is to highlight the potential of electrochemistry at the ITIES for analytical purposes, focusing on ITIES-based sensors for detection and quantification of chemically and biologically relevant (bio)molecules. We start by addressing the evolution of ITIES in terms of number of publications over the years along with an overview of their main applications (Chapter 1). Then, we provide a general historical perspective about pioneer voltammetric studies at water/oil systems (Chapter 2). After that, we discuss the most impacting improvements on ITIES sensing systems from both perspectives, set-up design (interface stabilization and miniaturization, selection of the organic solvent, etc.) and optimization of experimental conditions to improve selectivity and sensitivity (Chapter 3). In Chapter 4, we discuss the analytical applications of ITIES for electrochemical sensing of several types of analytes, including drugs, pesticides, proteins, among others. Finally, we highlight the present achievements of ITIES as analytical tool and provide future challenges and perspectives for this technology (Chapter 5).