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 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 possible fabrication of porous anodic oxide films on aluminium in ionic liquids based on choline dihydrogen citrate eutectic mixtures both with oxalic acid and isopropyl alcohol and ethylene glycol, has been investigated. The anodisation has been carried out in either potentiostatic or galvanostatic regime, at temperatures of 45-80 degrees C, for different process durations. Quite compact, uniform anodic alumina layers have been obtained. Based on AFM and SEM investigations, pore diameters between 50 and 80 nm and interpore distances in the range of 160-200 nm have been estimated, with values influenced by the electrolyte type and anodisation conditions. The highest anodisation rate of about 0.4 mu m min(-1) has been determined by applying operation temperatures of 60 degrees C. The recorded EIS spectra showed a pure capacitive behaviour and high anodic oxide resistances of 10(6)-10(7) omega cm(2) order.

Abstract A plasmonic nanostructure was constructed as a biorecognition element coupled to an optical sensing platform in sandwich format, targeting the hazelnut Cor a 14 allergen-encoding gene. The analytical performance of the genosensor presented a linear dynamic range between 100 amol L-1 and 1 nmol L-1 , a limit of detection (LOD) < 19.9 amol L-1 , and a sensitivity of 13.4 +/- 0.6 m.. The genosensor was successfully hybridized with hazelnut PCR products, tested with model foods, and further validated by real-time PCR. It reached a LOD <0.001% (10 mg kg(-1) ) of hazelnut in wheat material (corresponding to 1.6 mg kg(-1) of protein) and a sensitivity of 17.2 +/- 0.5 m. for a linear range of 0.001%-1%. Herein, a new genosensing approach is proposed as a highly sensitive and specific alternative tool with potential application in monitoring hazelnut as an allergenic food, protecting the health of sensitized/allergic individuals.

Abstract This work studies the antimicrobial activity of benzyldimethyldodecyl ammonium chloride (BDMDAC)-coated microparticles with distinct morphological structures. Functionalized microparticles were prepared by the layer-by-layer (LbL) self-assembly technique on hydroxyapatite (Hap), calcium carbonate (CaCO3) and glass beads (GB) cores. All particles were characterized, before and after functionalization, by Fourier-Transform Infrared Spectroscopy (FTIR), Brunner-Emmett-Teller (BET) and Scanning Electron Microscopy (SEM) analyses. Antimicrobial activity was tested against planktonic Pseudomonas fluorescens. Planktonic bacteria were exposed to 100 mg/L, 200 mg/L and 400 mg/L of BDMDAC-coated microparticles for 240 min. This strategy promoted a complete bacteria reduction at 200 mg/L for Hap microparticles after 240 min. No release of biocide was detected through HPLC analyses during 2 weeks, suggesting that bacteria inactivation may be attributed to a contact killing mechanism.

Abstract Dithiocarbazates comprise an important class of Schiff bases with remarkable biological applications due to the imine group present in their structure. However, full exploitation of the biological activity of 3-methyl-5-phenyl-pyrazoline-1-(S-benzyldithiocarbazate) (DTC) is limited due to its easy degradation and poor solubility in aqueous solutions. The loading of DTC into mesoporous silica nanoparticles (MSiNPs) can be an excellent strategy to improve the solubility of DTC in the aqueous medium. Therefore, the main goal of the present work was to design MSiNP-DTC and to evaluate the success of the loading process by measuring its physicochemical properties and evaluating the environmental safety of the new DTC formulation using different aquatic organisms, such as the microalgae Raphidocelis subcapitata, the macrophyte Lemna minor, and the marine bacterium Aliivibrio fischeri. DTC, MSiNP, and MSiNP-DTC concentrations ranging from 8.8 to 150 mg L-1 were tested for all the species, showing low toxicity against aquatic organisms. Loading DTC into MSiNPs caused a slight increase in the toxicity at the concentrations tested, only allowing for the estimation of the effect concentration causing a 20% reduction in bioluminescence or growth rate (EC20). Therefore, despite the potential of MSiNPs as a drug delivery system (DDS), it is of utmost importance to assess its impact on the safety of the new formulations.

Abstract Waste, in particular, biowaste, can be a valuable sourceof novelcarbon materials. Renewable carbon materials, such as biomass-derivedcarbons, have gained significant attention recently as potential electrodematerials for various electrochemical devices, including batteriesand supercapacitors. The importance of renewable carbon materialsas electrodes can be attributed to their sustainability, low cost,high purity, high surface area, and tailored properties. Fish wasterecovered from the fish processing industry can be used for energyapplications and prioritizing the circular economy principles. Herein,a method is proposed to prepare a high surface area biocarbon fromglycogen extracted from mussel cooking wastewater. The biocarbon materialswere characterized using a Brunauer-Emmett-Teller surfacearea analyzer to determine the specific surface area and pore sizeand by scanning electron microscopy coupled with energy-dispersiveX-ray analysis, Raman analysis, attenuated total reflectance Fouriertransform infrared spectroscopy, X-ray diffraction, X-ray photoelectronspectroscopy, and transmission electron microscopy. The electrochemicalcharacterization was performed using a three-electrode system, utilizinga choline chloride-based deep eutectic solvent (DES) as an eco-friendlyand sustainable electrolyte. Optimal time and temperature allowedthe preparation of glycogen-based carbon materials, with a specificsurface area of 1526 m(2) g(-1), a pore volumeof 0.38 cm(3) g(-1), and an associated specificcapacitance of 657 F g(-1) at a current density of1 A g(-1), at 30 degrees C. The optimal material wasscaled up to a two-electrode supercapacitor using a DES-based solid-stateelectrolyte (SSE@DES). This prototype delivered a maximum capacitanceof 703 F g(-1) at a 1 A g(-1) of currentdensity, showing 75% capacitance retention over 1000 cycles, deliveringthe highest energy density of 0.335 W h kg(-1) andpower density of 1341 W kg(-1). Marine waste can bea sustainable source for producing nanoporous carbon materials tobe incorporated as electrode materials in energy storage devices.

Abstract Many theoretical and experimental studies have been focused on the physicochemical properties of dense ionic fluids such as ionic liquids (ILs). However, less attention has been given to interfacial properties involving deep eutectic solvents (DES). The impact of the DES composition, hydrogen bond donor (HBD) structure, temperature, and electrode nature material on the DES-electrode vertical interactions remain vague. The lack of knowledge imposes significant constraints in proposing a suitable Electrical Double Layer model (EDL) to describe the DES at electrified interfaces. Measuring differential capacitance-potential curves is a strategy to assess the EDL structure and understand how ions interact with the electrode surface, which knowledge is fundamental to designing and optimizing electrochemical systems for various applications (e.g., energy storage devices). Accordingly, a set of choline chloride-based DESs was assessed containing distinct HBD at their eutectic composition (the poly-alcohol's 1,2-ethanediol, 1,2-propylene glycol, 1,3-propylene glycol, and the amide urea) against glassy carbon (GC), gold (Au), and the platinum (Pt) electrode at different temperatures. The differential capacitance-potential curves were found to vary significantly in shape in the three different electrode surfaces studied, ranging from camel shape (Au electrode), U-shape (GC), and asymmetric bell shape (polycrystalline Pt). The carboxylic malonic and oxalic acids were also assessed for a proper comparison to understand better the role of the HBD's functional group in shaping the electrode-electrolyte structure against the trend found with diol isomers. A suitable EDL model must inevitably accommodate interfacial properties assessed at the capacitive region, namely the influence of the surface chemistry, potential dependence, DES structure molecules, and temperature in shaping the electrified interfacial anatomy.

Abstract Over the past decade, molecular imprinting (MI) technologyhasmade tremendous progress, and the advancements in nanotechnology havebeen the major driving force behind the improvement of MI technology.The preparation of nanoscale imprinted materials, i.e., molecularlyimprinted polymer nanoparticles (MIP NPs, also commonly called nanoMIPs),opened new horizons in terms of practical applications, includingin the field of sensors. Currently, hydrogels are very promising forapplications in bioanalytical assays and sensors due to their highbiocompatibility and possibility to tune chemical composition, size(microgels, nanogels, etc.), and format (nanostructures, MIP film,fibers, etc.) to prepare optimized analyte-responsive imprinted materials.This review aims to highlight the recent progress on the use of hydrogelMIP NPs for biosensing purposes over the past decade, mainly focusingon their incorporation on sensing devices for detection of a fundamentalclass of biomolecules, the peptides and proteins. The review beginsby directing its focus on the ability of MIPs to replace biologicalantibodies in (bio)analytical assays and highlight their great potentialto face the current demands of chemical sensing in several fields,such as disease diagnosis, food safety, environmental monitoring,among others. After that, we address the general advantages of nanosizedMIPs over macro/micro-MIP materials, such as higher affinity towardtarget analytes and improved binding kinetics. Then, we provide ageneral overview on hydrogel properties and their great advantagesfor applications in the field of Sensors, followed by a brief descriptionon current popular routes for synthesis of imprinted hydrogel nanospherestargeting large biomolecules, namely precipitation polymerizationand solid-phase synthesis, along with fruitful combination with epitopeimprinting as reliable approaches for developing optimized protein-imprintedmaterials. In the second part of the review, we have provided thestate of the art on the application of MIP nanogels for screeningmacromolecules with sensors having different transduction modes (optical,electrochemical, thermal, etc.) and design formats for single use,reusable, continuous monitoring, and even multiple analyte detectionin specialized laboratories or in situ using mobiletechnology. Finally, we explore aspects about the development of thistechnology and its applications and discuss areas of future growth.