Publications

Abstract <jats:p>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.</jats:p>

Abstract A novel, straightforward, and environmentally friendly direct coupling procedure to immobilize carbohydrates on solid supports is presented. A characterization study showed that all amino groups on solid supports participated in the linkage with a carbohydrate unit, implicating that the surface load can be easily adjusted by tuning the amination coverage of the surface. Most importantly, the integrity of the cyclic conformation of the linked sugar unit was demonstrated, a feature that is critical for most of the possible applications of carbohydrate-functionalized surfaces. Furthermore, carbohydrate-immobilized submicron particles synthesized by the direct coupling method, on which lectin profiling experiments were conducted, validated the successfulness of our simplistic approach.

Abstract The objective of this work was the exploration of low calcination temperature ranges (< 350 degrees C) to obtain molecularly imprinted microspheres (MIM) with a high crystallinity as anatase, in cooperation of an acidic pretreatment aiming at the preservation of the hollow shape and also of the selective binding sites. It was confirmed the possibility of obtaining bilirubin-imprinted crystalline TiO2 microspheres (highly crystalline anatase, as confirmed by XRD) exhibiting higher photocatalytic efficiency associated especially with the hollow shape and calcination at lower temperatures (200 degrees C or 250 degrees C). It was with the calcination temperature of 250 degrees C that the highest photocatalytic efficiency was obtained, under UV irradiation, associated with the highest adsorption selectivity (alpha(K) = 19) and degradation selectivity (alpha(k) = 2.7) observed for the degradation of the template against a closely related analogue compound.

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 Graphene and its derivatives are generally portrayed as electron transfer enhancers that effectively boost the electrochemical response of classic electrodes for applications in renewable energy, electronics, or analysis (amongst others). However, a number of fundamental studies have challenged this view. In certain reports, not only could no beneficial effect be demonstrated, but the opposite was concluded. If we want to advance towards a more rational design of high-performance electrode devices, these discrepancies need to be cleared and the fundamental aspects of electron transfer reactions through graphene-electrodes further understood. The present study contributes to this cause by exploring the relationships between the structure and morphological appearance of graphene films and their electrochemical performance in fundamental proof-of-concept experiments. The results unveil that important differences in the structure and morphology of the films (which are tightly related to the composition and load of graphene materials) govern the electrochemical response of the modified electrodes. Thereby, a possible explanation for the apparently contradictory conclusions reported in the literature is provided.

Abstract Optosensing chitosan-based membranes have been applied for the detection of heavy metals, especially in drinking water. The novelty of this study is based on the use of sulphated polysaccharides, in such optosensing membranes, aiming at an improved analytical performance. The sulphated polysaccharides, such as ulvan, fucoidan and chondroitin sulfate, were extracted from by-products and wastes of marine-related activities. The membranes were developed for the analysis of aluminum. The variation in the visible absorbance of the sensor membranes after the contact between the chromophore and the aluminum cation was studied. The membranes containing sulphated polysaccharides showed improved signals when compared to the chitosan-only membrane. As for the detection limits for the membranes containing ulvan, fucoidan and chondroitin sulfate, 0.17 mg L-1, 0.21 mg L-1 and 0.36 mg L-1 were obtained, respectively. The values were much lower than that obtained for the chitosan-only membrane, 0.52 mg L-1, which shows the improvement obtained from the sulphated polysaccharides. The results were obtained with the presence of CTAB in analysis solution, which forms a ternary complex with the aluminum cation and the chromophore. This resulted in an hyperchromic and batochromic shift in the absorption band. When in the presence of this surfactant, the membranes showed lower detection limits and higher selectivity.

Abstract The possibility of generating organically modified hollow TiO2 microspheres via a simple sol-gel synthesis was demonstrated for the first time in this work. A mixture of titania precursors, including an organically modified precursor, was used to obtain methyl-modified hollow TiO2 microspheres selective for bilirubin by the molecular imprinting technique (Methyl-HTM-MIM). Methyl-HTM-MIM were prepared by a sol-gel method using titanium (IV) isopropoxide (TTIP), and methyltitanium triisopropoxide (MTTIP) as precursors. Two ratios of titania precursors were tested (1/6 and 1/30 mol(MTTIP)/mol(TTIP)). With the characterization results obtained by the SEM and ATR-FTIR techniques, it was possible to establish that only the 1/30 mol(MTTIP)/mol(TTIP) ratio allowed for the preparation of hollow spheres with a reasonably homogeneous methylated-TiO2 shell. It was possible to obtain a certain degree of organization of the hybrid network, which increased with calcination temperatures. By adjusting isothermal adsorption models, imprinting parameters were determined, indicating that the new methylated microspheres presented greater selectivity for bilirubin than the totally inorganic hollow TiO2 microspheres. The effectiveness of the molecular imprinting technique was proven for the first time in an organically modified titania material, with imprinting factor values greater than 1.4, corresponding to a significant increase in the maximum adsorption capacity of the template represented by the molecularly imprinted microspheres. In summary, the results obtained with the new methyl-HTM-MIM open the possibility of exploring the application of these microspheres for selective sorption (separation or sensing, for example) or perhaps even for selective photocatalysis, particularly for the degradation of organic compounds.

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 A new sensing platform based on long-period fiber gratings (LPFGs) for direct, fast, and selective detection of human immunoglobulin G (IgG; Mw = 150 KDa) was developed and characterized. The transducer's high selectivity is based on the specific interaction of a molecularly imprinted polymer (MIPs) design for IgG detection. The sensing scheme is based on differential refractometric measurements, including a correction system based on a non-imprinted polymer (NIP)-coated LPFG, allowing reliable and more sensitive measurements, improving the rejection of false positives in around 30%. The molecular imprinted binding sites were performed on the surface of a LPFG with a sensitivity of about 130 nm/RIU and a FOM of 16 RIU-1. The low-cost and easy to build device was tested in a working range from 1 to 100 nmol/L, revealing a limit of detection (LOD) and a sensitivity of 0.25 nmol/L (0.037 mu g/mL) and 0.057 nm.L/nmol, respectively. The sensor also successfully differentiates the target analyte from the other abundant elements that are present in the human blood plasma.

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.