Publications

Abstract This work reports the development of a simple and rapid electrochemical immunosensor for the determination of breast cancer biomarker Cancer Antigen 15-3 (CA 15-3). Disposable and cost-effective chips, consisting of gold screen-printed electrodes (AuSPEs), were used to develop the portable electrochemical devices for monitoring the biomarker in point-of-care (PoC), under clinical context. The biosensor preparation consisted of two simple steps. First, a self-assembled monolayer (SAM) of mercaptosuccinic acid (MSA) was formed at the AuSPE surface. Then, the CA 15-3 antibody was covalently bound to the carboxylic groups standing at the electrode surface using EDC/NHS chemistry. The performance of the developed immunosensor was evaluated by assessing the sensor sensitivity, linear response interval, selectivity and detection limit (LOD). The developed immunosensor provided a wide linear concentration range (from 1.0 to 1000 U mL(-1)) and low detection levels were achieved (LOD of 0.95 U mL(-1)), enabling the sensitive detection of the cancer biomarker at clinically relevant levels, using square wave voltammetry (SWV) as electroanalytical technique. Moreover, selectivity studies performed against other cancer biomarkers (CA 125 and CA 19-9) revealed that the antibody has high selectivity for CA 15-3 antigen. The immunosensor was applied to the quantification of CA 15-3 in artificial serum samples with satisfactory results.

Abstract In this work, we describe an innovative methodology based on combined surface plasmon resonance (SPR) and electrochemical responses (eSPR) in the same immunoassay for screening CA 15-3 cancer biomarker with high sensitivity (and selectivity), in a very simple, label-free, accurate, and fully automated manner. Detection was achieved by performing two simple steps. In the first step, direct SPR was used to monitor CA 15-3 interaction with surface immobilized antibody. Two linear response ranges were obtained and the detection limit achieved is poor (LOD of 21 U mL(-1)). However, in the second detection step, electrochemical measurements at the SPR gold surface were performed to measure the decrease of redox probe peak current upon antigen-antibody interaction, providing a suitable amplification strategy to lower detection levels of CA 15-3 (LOD of 0.0998 U mL(-1)), without the need of additional complex and/or expensive amplification steps to enhance the sensitivity. Moreover, selectivity studies were performed against other common cancer biomarkers and the results showed that the eSPR immunosensor is selective for the CA 15-3 protein. Finally, the clinical applicability of the developed eSPR biosensing methodology was successfully applied to detect CA 15-3 in human serum samples at clinically relevant levels due to the high sensitivity of electrochemical readout. The same concept may be further extended to other proteins of interest.

Abstract In this study, Co-TiO2 nanoparticles were successfully synthesized using sol-gel and precipitation methods. The effect of Co amount on the physicochemical properties of these nanomaterials was investigated using various techniques. The obtained results showed that the structural and optical properties of the synthesized Co-TiO2 nanomaterials depended closely on the weight percent of Co added to TiO2. It was found that, for 1%Co-TiO2, a substitution of Ti4+ and Co2+/Co3+ within the lattice of TiO2 was happened. The results of the photocatalytic degradation of methyl orange (MO) experiments carried out in the presence of the as prepared nanomaterials showed that under visible light, the sample 1%Co-TiO2 exhibited the best MO conversion. The enhanced photocatalytic activity has been attributed to the efficient charge separation of electrons and holes. The mechanistic studies revealed that O-2(center dot-), h(+) and OH center dot are the major active species, and a possible mechanism degradation pathway of MO dye is proposed.

Abstract Although Solanum nigrum L. is a phytoremediator for different metals, its growth and physiology are still compromised by toxic levels of zinc (Zn). Thus, the development of eco-friendly strategies to enhance its tolerance, maintaining remediation potential is of special interest. This study evaluated the potential of 24-epibrassinolide (24-EBL) to boost S. nigrum defence against Zn towards a better growth rate and remediation potential. After 24 days of exposure, the results revealed that Zn-mediated inhibitory effects on biomass and biometry were efficiently mitigated upon application of 24-EBL, without affecting Zn accumulation. The evaluation of oxidative stress markers reported that Zn excess stimulated the accumulation of superoxide anion (O-2(center dot-)), but reduced hydrogen peroxide (H2O2) levels, while not altering lipid peroxidation (LP). This was accompanied by an up-regulation of the antioxidant system, especially proline, superoxide dismutase (SOD) and ascorbate peroxidase (APX) in both organs, and ascorbate in roots of Zn-exposed plants. Foliar application of 24-EBL, however, induced distinctive effects, lowering proline levels in both organs, as well as APX activity in shoots and SOD in roots, whilst stimulating GSH and total thiols in both organs, as well as SOD and APX activity, in shoots and in roots, respectively. Probably due to a better antioxidant efficiency, levels of O-2(center dot-) and H2O2 in pre-treated plants remained identical to the control, while LP further decreased in shoots. Overall, our results indicate a protective effect of 24-EBL on S. nigrum response to excess Zn, contributing for a better tolerance and growth rate, without disturbing its phytoremediation potential.

Abstract A hybrid conjugate of reduced graphene oxide/ferrous-ferric oxide nanoparticles (rGO-Fe3O4 NPs) is characterized and assembled with chitosan and laccase to form a layered functional superstructure. After its characterization by field-effect scanning electron microscopy, energy-dispersive X-ray analysis, X-ray photoelectron spectroscopy, attenuated total reflectance Fourier transform infrared, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS), the nanocomposite has been deposited on glassy carbon for the enzyme-mediated electrochemical determination of the endocrine disruptor bisphenol A (BPA). Proof-of-concept assays conducted by using CV, EIS, and square wave voltammetry reveal that the enzymatic biosensor provides linear response in a wide range of BPA concentrations (6-228 ppb), very high sensitivities, and excellent durability (over 1-month storage). Using amperometric detection, remarkable sensitivities (2080 mu A mu M-1 cm(-2)) and detection limits (18 nM) are attained. Applications to real samples of bottled water proved feasible with recoveries in the range 107-124%.

Abstract The structure of the title quinoline carboxamide derivative, C26H25N3O, is described. The quinoline moiety is not planar as a result of a slight puckering of the pyridine ring. The secondary amine has a slightly pyramidal geometry, certainly not planar. Both intra- and intermolecular hydrogen bonds are present. Hirshfeld surface analysis and lattice energies were used to investigate the intermolecular interactions.

Abstract A study on the Pb(II) imprinting performed within mesoporous sulphated biopolymer/siloxane composites, prepared in media containing deep eutectic solvent (DES), is described. In general, the process of imprinting resulted in greatly increased surface areas relatively to the corresponding nonimprinted composites [up to fivefold (from 76 m(2) g(-1) to 360 m(2) g(-1)) for fucoidan (Fuc) and up to twofold (from 208 m(2) g(-1) to 351 m(2) g(-1)) for chondroitin sulfate (CS) composites], the diminishing of mean pore size (from 3.3-4.6 nm to 2.9-3.4), and higher biopolymer contents (from mass fractions of 0.42-0.52 to 0.46-0.68). The sorption features depended a great deal on the biopolymer/DES combination. The best CS composite, allowed for 12% capacity and 20% binding strength, as well as Pb(II)/Cd(II) selectivity enhancements. The largest of the capacities was obtained with the imprinted Fuc/DES-E composite, 86 mg g(-1), a 10% increase. Concerning the selectivity [Pb(II) versus Cd(II)], there was a significant increase for the CS composites (from 1.0-1.1 (alpha(qmax))/1.1-1.2 (alpha(K)) to 1.3-1.4 (alpha(qmax))/1.3-1.6 (alpha(K))]. In particular, the DES-E CIC presented high selectivity factors (alpha(qmax) 3.0/alpha(K) 3.2) in line with those of the microporous version (alpha(qmax) 2.0/alpha(K) 3.3) but showing a significant increase in terms of the alpha(qmax) selectivity. (c) 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 137, 48842.

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 The study of the phase behaviour of binary mixtures of fatty acid methyl esters (FAME) and alkanes are here studied to understand the behaviour of the mineral diesel/biodiesel blends. Six binary mixtures of the most common saturated methyl esters (methyl stearate or methyl palmitate) with a saturated alkane (hexadecane, octadecane or eicosane) were evaluated by differential scanning calorimetry (DSC), X-ray diffraction (XRD) and optical microscopy. The binary mixtures studied show a more complex phase behaviour than previously reported, which it is shown to be dependent of the size difference between the alkyl chain length of the esters and the alkanes. It was found that in mixtures with equal alkyl chain length a co-crystal is formed, and when the alkane chain length is larger than in the FAME by two methylene groups the formation of a solid-solution increasing significantly the solid phase stability is observed. The results and conclusions derived from the phase behaviour of this set of binary mixtures, between alkanes and methyl esters, can be used as a model for the interpretation of the cloud and pour points increase in biodiesel blends (in special the ones with a rich fraction of methyl palmitate or methyl stearate when combined with mineral diesel with high content of octadecane or eicosane respectively).

Abstract Mobile devices seem to be more present in language education and classrooms, but the role of such technologies on educator's identity and practice is still at its early stages. This investigation aimed to gather a better understanding around the use of mobile-assisted language learning (MALL) through the lenses of educators that base their practices on the second language acquisition (SLA) theory, what are their perceptions on the relevancy of mobile devices for language acquisition and its potential role on their professional identities (as well as their views on using mobile technologies to promote opportunities for second language acquisition to occur). Since second language acquisition education and professional identity are not covered alongside in MALL literature, the goal of this research was to gather data on the perceptions around mobile devices used for language acquisition from the educators' perspective and their professional identity. A semi-structured interview script with open questions was developed to cover all three main topics as well as to promote participants' insights around the current use of mobile technologies in their language education scenarios. The research included 12 second language acquisition educators from Brazil, acting in different educational scenarios were selected to be interviewed via Skype. The data gathered was analyzed using NVivo and interpreted by using the guidelines provided by grounded theory. Results showed that: a) participants consider mobile devices as ad-value for language acquisition when they recognize relevancy in using such devices in what they describe as "acquisition opportunities". The use is not standardized and varies according to the educator. The lack of support from schools is accounted as a factor for non-use. b) Second language educators view themselves as facilitators between students and language. They understand that their professional identities are in constant change by social, cultural, and economic factors, and adding new tools and methodologies to their practices are expected; therefore, mobile devices are not viewed as threats to educators' professional identity. However, participants showed concerns that the mandatory use of mobile devices and technologies in classes without previous training and debate around its proper use might contribute to an unwanted professional identity change. c) Participants do not consider themselves proficient in what they understand to be an ideal use of mobile devices for language acquisition. However, this lack of understanding does not impede them from using mobile devices as a pedagogical instrument as they seem fit. The discussion focuses on the paradox between the relevancy recognized by educators in mobile devices for language acquisition and their lack of repertoire for the use of such devices.