Publications

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).

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 Background: Patients with immune-mediated inflammatory diseases (IMIDs) treated with immunomodulatory therapy present an increased susceptibility to infections. Vaccination is a crucial element in the management of IMID patients; however, rates remain suboptimal. This study intended to clarify the adherence to prescribed vaccines. Materials and methods: This prospective cohort study included 262 consecutive adults with inflammatory bowel disease and rheumatological diseases who underwent an infectious diseases evaluation before initiating or switching immunosuppressive/biological therapy. Vaccine prescription and adherence were assessed during an infectious diseases (ID) consultation using a real-world multidisciplinary clinical project. Results: At baseline, less than 5% had all their vaccines up-to-date. More than 650 vaccines were prescribed to 250 (95.4%) patients. The most prescribed were pneumococcal and influenza vaccines, followed by hepatitis A and B vaccines. Adherence to each of the vaccines ranged from 69.1-87.3%. Complete adherence to vaccines occurred in 151 (60.4%) patients, while 190 (76%) got at least two-thirds of them. Twenty patients (8%) did not adhere to any of the vaccines. No significant differences were found in the adherence rates of patients with different sociodemographic and health-related determinants. Conclusions: ID physicians can play a role in the process of increasing vaccine prescription and adherence. However, more data on patients' beliefs and vaccine hesitancy, along with mobilization of all health care professionals and adequate local interventions, shall be considered to improve vaccine adherence.

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 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 Amyotrophic lateral sclerosis (ALS) is a devastating neurodegenerative disease with a rapid progression and no effective treatment. Metabolic and mitochondrial alterations in peripheral tissues of ALS patients may present diagnostic and therapeutic interest. We aimed to identify mitochondrial fingerprints in lymphoblast from ALS patients harboring SOD1 mutations (mutSOD1) or with unidentified mutations (undSOD1), compared with age-/sex-matched controls. Three groups of lymphoblasts, from mutSOD1 or undSOD1 ALS patients and age-/sex-matched controls, were obtained from Coriell Biobank and divided into 3 age-/sex-matched cohorts. Mitochondria-associated metabolic pathways were analyzed using Seahorse MitoStress and ATP Rate assays, complemented with metabolic phenotype microarrays, metabolite levels, gene expression, and protein expression and activity. Pooled (all cohorts) and paired (intra-cohort) analyses were performed by using bioinformatic tools, and the features with higher information gain values were selected and used for principal component analysis and Naive Bayes classification. Considering the group as a target, the features that contributed to better segregation of control, undSOD1, and mutSOD1 were found to be the protein levels of Tfam and glycolytic ATP production rate. Metabolic phenotypic profiles in lymphoblasts from ALS patients with mutSOD1 and undSOD1 revealed unique age-dependent different substrate oxidation profiles. For most parameters, different patterns of variation in experimental endpoints in lymphoblasts were found between cohorts, which may be due to the age or sex of the donor. In the present work, we investigated several metabolic and mitochondrial hallmarks in lymphoblasts from each donor, and although a high heterogeneity of results was found, we identified specific metabolic and mitochondrial fingerprints, especially protein levels of Tfam and glycolytic ATP production rate, that may have a diagnostic and therapeutic interest.