Publications

Abstract Artificial receptors that mimic their natural biological counterparts have several advantages, such as lower production costs and increased shelf-life stability/versatility, while overcoming the ethical issues related to raising antibodies in animals. In this work, the proposed tailor-made molecularly imprinted polymer (MIP)-allergen receptors aimed at substituting or even transcending the performance of biological antibodies. For this purpose, a MIP was proposed as an artificial antibody for the recognition of hazelnut Cor a 14-allergen. The target protein was grafted onto the conducting polypyrrole receptor film using gold screen-printed electrodes (Au-SPE). The electrochemical assessment presented a linear response for the dynamic range of 100 fg mL(-1)-1 mu g mL(-1) and a LOD of 24.5 fg mL(-1), as determined by square wave voltammetry from the calibration curves prepared with standards diluted in phosphate buffer. Surface plasmon resonance (SPR) was used as a secondary transducer to evaluate the performance of the Cor a 14-MIP sensor, enabling a linear dynamic range of 100 fg mL(-1) - 0.1 mu g mL(-1) and a LOD of 18.1 fg mL(-1). The selectivity of the tailored-made Cor a 14-MIP was tested against potentially cross-reactive plant/animal species based on the rebinding affinity (Freundlich isotherm-K-F) of homologues/similar proteins, being further compared with custom-made polyclonal anti-Cor a 14 IgG immunosensor. Results evidenced that the MIP mimics the biorecognition of biological antibodies, presenting higher selectivity (only minor cross-reactivity towards walnut and Brazil nut 2S albumins) than the Cor a 14/anti-Cor a 14 IgG immunosensor. The application of electrochemical Cor a 14-MIP sensor to model mixtures of hazelnut in pasta enabled quantifying hazelnut down to 1 mg kg(-1) (corresponding to 0.16 mg kg(-1) of hazelnut protein in the matrix). To the best of our knowledge, Cor a 14-MIP is the first sensor based on an artificial/synthetic biorecognition platform for the specific detection of hazelnut allergens, while presenting high-performance parameters with demonstrated application in food safety management.

Abstract A suitable dispersion of carbon materials (e.g., carbon nanotubes (CNTs)) in an appropriate dispersant media, is a prerequisite for many technological applications (e.g., additive purposes, functionalization, mechanical reinforced materials for electrolytes and electrodes for energy storage applications, etc.). Deep eutectic solvents (DES) have been considered as a promising "green" alternative, providing a versatile replacement to volatile organic solvents due to their unique physical-chemical properties, being recognized as low-volatility fluids with great dispersant ability. The present work aims to contribute to appraise the effect of the presence of MWCNTs and Ag-functionalized MWCNTs on the physicochemical properties (viscosity, density, conductivity, surface tension and refractive index) of glyceline (choline chloride and glycerol, 1:2), a Type III DES. To benefit from possible synergetic effects, AgMWCNTs were prepared through pulse reverse electrodeposition of Ag nanoparticles into MWCNTs. Pristine MWCNTs were used as reference material and water as reference dispersant media for comparison purposes. The effect of temperature (20 to 60 degrees C) and concentration on the physicochemical properties of the carbon dispersions (0.2-1.0 mg cm(-3)) were assessed. In all assessed physicochemical properties, AgMWCNTs outperformed pristine MWCNTs dispersions. A paradoxical effect was found in the viscosity trend in glyceline media, in which a marked decrease in the viscosity was found for the MWCNTs and AgMWCNTs materials at lower temperatures. All physicochemical parameters were statistically analyzed using a two-way analysis of variance (ANOVA), at a 5% level of significance.

Abstract Two immunosensors were advanced to target hazelnut Cor a 14 based on electrochemical and optical transduction. Both approaches were developed with two types of custom-made antibodies, namely anti-Cor a 14 IgG (rabbit) and anti-Cor a 14 IgY (hen's egg) targeting the Cor a 14 allergen. Antibody immobilisation was performed via EDC/NHS onto disposable screen-printed electrodes. The detection limit (LOD) of the electrochemical immunoassay for Cor a 14 was 5-times lower than the optical, being down to 0.05 fg mL-1 with a dynamic range of 0.1 fg mL-1 to 0.01 ng mL-1. Antibody selectivity was verified against non-target 2S albumins (potential crossreactive plant species). Anti-Cor a 14 IgY exhibited the best specificity, presenting minor cross-reactivity with peanut/walnut. Preliminary results of the application of anti-Cor a 14 IgY electrochemical immunosensor to incurred foods established a LOD of 1 mg kg- 1 of hazelnut in wheat (0.16 mg kg- 1 hazelnut protein).

Abstract The urgent need to reduce the consumption of fossil fuels drives the demand for renewable energy and has been attracting the interest of the scientific community to develop materials with improved energy storage properties. We propose a sustainable route to produce nanoporous carbon materials with a high-surface area from commercial graphite using a dry ball-milling procedure through a systematic study of the effects of dry ball-milling conditions on the properties of the modified carbons. The microstructure and morphology of the dry ball-milled graphite/carbon composites are characterized by BET (Brunauer-Emmett-Teller) analysis, SEM (scanning electron microscopy), ATR-FTIR (attenuated total reflectance-Fourier transform infrared spectroscopy) and Raman spectroscopy. As both the electrode and electrolyte play a significant role in any electrochemical energy storage device, the gravimetric capacitance was measured for ball-milled material/glassy carbon (GC) composite electrodes in contact with a deep eutectic solvent (DES) containing choline chloride and ethylene glycol as hydrogen bond donor (HBD) in a 1:2 molar ratio. Electrochemical stability was tracked by measuring charge/discharge curves. Carbons with different specific surface areas were tested and the relationship between the calculated capacitance and the surface treatment method was established. A five-fold increase in gravimetric capacitance, 25.27 F center dot g(-1) (G40) against 5.45 F center dot g(-1), was found for commercial graphene in contact with DES. Optimal milling time to achieve a higher surface area was also established.

Abstract Carbon nanotubes (CNTs) are receiving special attention due to their remarkable thermal, electrical, and mechanical properties. The present work reports an innovative synthesis procedure to decorate MWCNTs with silver nanoparticles (Ag-NPs) via pulsed reverse deposition technique using a deep eutectic solvent (DES) based on choline chloride and glycerol as an electrolyte at room temperature, not requiring any previous surface modification of MWCNTs. MWCNTs decorated with Ag-NPs disclose a significant enhancement of their electrochemical performance as demonstrated by the increase of electrode stability and specific capacitance. Electrochemical characterization of the composite material was performed using cyclic voltammetry and charge/discharge curves, achieving a specific capacitance up to 28.50 F. g-1, against 4.70 F. g-1 for the commercial MWCNTs in a three-electrode system. Retention of the specific capacitance up to 99% for the Ag-MWCNTs composites compared with a value of 78% for electrodes modified with commercial MWCNTs. The Ag-MWCNTs composites were characterized through SEM/EDX analysis, ultrahighresolution STEM, in which the Z - Contrast image was collected, and Raman analysis to prove the successful attachment of the Ag-NPs to the MWCNTs surface. AFM was performed to evaluate the conductivity of the composites. (c) 2021 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Abstract The air-ionic liquid interface for a series of ionic liquids involving imidazolium cations [C(n)mim] with different alkyl chain lengths (n = 2, 4, 6, 8, 10, and 12) and the same [NTf2] imide anion has been studied by polarization-resolved second harmonic generation (SHG). An increase as a function of the alkyl chain length of the orientational parameter reveals the increasing ordering of the air-pure ionic liquid interfaces although it is not possible to disentangle the change in mean tilt angle from a change in the tilt angle probability distribution width. Besides, the study of the air-mixed ([C(12)mim])(x)([C(2)mim])(1-x)[NTf2] ionic liquid interface clearly demonstrates the interfacial nonideality of the mixed ionic liquids. The long alkyl chain cation perturbs the interface as seen from the orientational parameter and displaces the short alkyl chain one for bulk mixture contents as low as 10%. At higher long alkyl chain cation bulk mixture contents, the interface behaves close to a pure long alkyl chain ionic liquid.

Abstract Metal and alloys electrodeposition from aqueous electrolytes is restricted due to the narrow electrochemical window and hydrogen evolution. To overcome these disadvantages, over the past years, ionic liquids (ILs) and deep eutectic solvents (DES) based on choline chloride have been successfully applied for the electrodeposition of different metals. Tin (Sn) layers applied to automotive or decorative plating are thought of as ecological alternatives to exchange lead and nickel/chromium coatings. Over the past few years, the attention drawn by metallic alloys and composites, namely Sn alloys (nickel, indium, copper, zinc…) and Sn-carbon materials composites, has increased due to the possibility of applying these materials as anodes for lithiumion batteries. This review will highlight the leading research regarding the electrodeposition of Sn and several alloys and carbon composites, emphasizing the morphological changes of the alloy combinations using DESs as electrolytes.

Abstract Considering the high incidence level and mortality rate of ovarian cancer, particularly among the European female population, the carbohydrate antigen 125 (CA-125) was selected as the protein target for this study for the development of a MIP-based biosensor. This work presents the development of molecular imprinting polymers (MIPs) on gold electrode surface for CA-125 biomarker recognition. The preparation of the CA-125 imprinting was obtained by electropolymerization of pyrrole (Py) monomer in a gold electrode using cyclic voltammetry (CV) in order to obtain highly selective materials with great molecular recognition capability. The quantification of CA-125 biomarker was made through the comparison of two methods: electrochemical (square wave voltammetry -SWV) and optical transduction (surface plasmon resonance -SPR). SWV has been widely used in biological molecules analysis since it is a fast and sensitive technique. In turn, SPR is a non-destructive optical technique that provides high-quality analytical data of CA-125 biomarker interactions with MIP. Several analytical parameters, such as sensitivity, linear response interval, and detection limit were determined to proceed to the performance evaluation of the electrochemical and optical transduction used in the development of the CA-125 biosensor. The biosensor based in the electrochemical transduction was the one that presented the best analytical parameters, yielding a good selectivity and a detection limit (LOD) of 0.01 U/mL, providing a linear concentration range between 0.01 and 500 U/mL. This electrochemical biosensor was selected for the study and it was successfully applied in the CA-125 analysis in artificial serum samples with recovery rates ranging from 91 to 105% with an average relative error of 5.8%.

Abstract Nano carbons, such as graphene and carbon nanotubes, show very interesting electrochemical properties and are becoming a focus of interest in many areas, including electrodeposition of carbon-metal composites for battery application. The aim of this study was to incorporate carbon materials (namely oxidized multi-walled carbon nanotubes (ox-MWCNT), pristine multi-walled carbon nanotubes (P-MWCNT), and reduced graphene oxide (rGO)) into a metallic tin matrix. Formation of the carbon-tin composite materials was achieved by electrodeposition from a choline chloride-based ionic solvent. The different structures and treatments of the carbon materials will create metallic composites with different characteristics. The electrochemical characterization of Sn and Sn composites was performed using chronoamperometry, potentiometry, electrochemical impedance, and cyclic voltammetry. The initial growth stages of Sn and Sn composites were characterized by a glassy-carbon (GC) electrode surface. Nucleation studies were carried out, and the effect of the carbon materials was characterized using the Scharifker and Hills (SH) and Scharifker and Mostany (SM) models. Through a non-linear fitting method, it was shown that the nucleation of Sn and Sn composites on a GC surface occurred through a 3D instantaneous process with growth controlled by diffusion. According to Raman and XRD analysis, carbon materials were successfully incorporated at the Sn matrix. AFM and SEM images showed that the carbon incorporation influences the coverage of the surface as well as the size and shape of the agglomerate. From the analysis of the corrosion tests, it is possible to say that Sn-composite films exhibit a comparable or slightly better corrosion performance as compared to pure Sn films.