Publications

Abstract The present work is focused on determining the enthalpy of formation of several derivatives of amino-1,2,4-triazoles. Experimentally, the enthalpies of formation of the crystalline phase and the enthalpies of sublimation of 3-amino- and 3,5-diamino-1H-1,2,4-triazole were derived, respectively, from static-bomb combustion calorimetry and Calvet microcalorimetry or Knudsen effusion measurements. For 4-amino-4H-1,2,4-triazole, only the enthalpy of sublimation was measured. Gas-phase standard molar enthalpies of formation were also estimated using theoretical calculations performed with the G3(MP2) composite approach. The very good agreement of these estimates with the experimental results, support the extension of this study to the estimate of this property for the remaining compounds not studied experimentally. The results obtained are interpreted in terms of structural contributions.

Abstract Nanoparticle-based plasmonic optical fiber sensors can exhibit high sensing performance, in terms of refractive index sensitivities (RISs). However, a comprehensive understanding of the factors governing the RIS in this type of sensor remains limited, with existing reports often overlooking the presence of surface plasmon resonance (SPR) phenomena in nanoparticle (NP) assemblies and attributing high RIS to plasmonic coupling or waveguiding effects. Herein, using plasmonic optical fiber sensors based on spherical Au nanoparticles, we investigate the basis of their enhanced RIS, both experimentally and theoretically. The bulk behavior of assembled Au NPs on the optical fiber was investigated using an effective medium approximation (EMA), specifically the gradient effective medium approximation (GEMA). Our findings demonstrate that the Au-coated optical fibers can support the localized surface plasmon resonance (LSPR) as well as SPR in particular scenarios. Interestingly, we found that the nanoparticle sizes and surface coverage dictate which effect takes precedence in determining the RIS of the fiber. Experimental data, in line with numerical simulations, revealed that increasing the Au NP diameter from 20 to 90 nm (15% surface coverage) led to an RIS increase from 135 to 6998 nm/RIU due to a transition from LSPR to SPR behavior. Likewise, increasing the surface coverage of the fiber from 9% to 15% with 90 nm Au nanoparticles resulted in an increase in RIS from 1297 (LSPR) to 6998 nm/RIU (SPR). Hence, we ascribe the exceptional performance of these plasmonic optical fibers primary to SPR effects, as evidenced by the nonlinear RIS behavior. The outstanding RIS of these plasmonic optical fibers was further demonstrated in the detection of thrombin protein, achieving very low limits of detection. These findings support broader applications of high-performance NP-based plasmonic optical fiber sensors in areas such as biomedical diagnostics, environmental monitoring, and chemical analysis. (c) 2024 Chinese Laser Press

Abstract Ethanol plays a crucial role in modern industrial processes and consumer products. Despite its presence in human activity, short and long-term exposure to gaseous ethanol poses risks to health conditions and material damage, making the control of its concentration in the atmosphere of high importance. Ethanol optical sensors based on electromagnetic surface waves (ESWs) are presented, with sensitivity to ethanol vapours being achieved by the inclusion of ethanol-adsorptive zinc oxide (ZnO) layers. The changes in optical properties modulate the resonant conditions of ESWs, enabling the tracking of ethanol concentration in the atmosphere. A comprehensive comparative study of sensor performance is carried out between surface plasmon resonance (SPR) and Bloch surface wave (BSW) based sensors. Sensor efficiency is simulated by transfer matrix method towards optimized figures of merit (FoM). Preliminary results validate ethanol sensitivity of BSW based sensor, showcasing a possible alternative to electromagnetic and plasmonic sensors. © The Authors.

Abstract Structural health monitoring (SHM) of reinforced concrete structures (RCS) is crucial for mitigating the consequences of their deterioration. By identifying and addressing the issues early, SHM helps reduce environmental impact, safeguard lives, and enhance economic resilience. Rebar corrosion is a leading cause of early RCS decay and optical fibre sensors (OFS) have been employed for its monitoring. Reflection optrodes using optical fibres where the tip is coated with iron (Fe) thin films offer a robust, long-lasting and straightforward solution. This study investigates the tracking of spectral changes during the Fe thin film corrosion, which has been neglected in the literature, in favour of tracking reflection changes from thin film spalling. A multimode fibre tip, coated with a thin Fe layer embedded in concrete, allows spectral changes to be observed during corrosion. A 100 nm thick Fe film was deposited using radio frequency magnetron sputtering on polished fibre tips. Corrosion was induced by applying salted water drops and allowing the fibre tip to dry. Corrosion monitoring was successful for both air-exposed and cement-embedded tips, with results compared to reflection simulations of Fe, Fe2O3, and Fe2O3 thin films. This study supports monitoring at different wavelengths, enhancing robustness, cost-effectiveness and earlier detection. © The Authors.

Abstract This work studies the formation of deep eutectic solvents formed by one active pharmaceutical ingredient (quinine, pyrimethamine, or 2-phenylimidazopyridine) and a second component potentially acting as an excipient (betaine, choline chloride, tetramethylammonium chloride, thymol, menthol, gallic acid, vanillin, acetovanillone, 4-hydroxybenzaldehyde, syringaldehyde, propyl gallate, propylparaben, or butylated hydroxyanisole), aiming to address challenges regarding drug solubility, bioavailability, and permeability. A preliminary screening was carried out using the thermodynamic model COSMO-RS, narrowing down the search to three promising excipients (thymol, propyl gallate, and butylated hydroxyanisole). Nine solid-liquid equilibrium (SLE) phase diagrams were experimentally measured combining the three model drugs with the screened excipients, and using a combination of a visual melting method and differential scanning calorimetry. Negative deviations from thermodynamic ideality were observed in all nine systems. Furthermore, a total of four new cocrystals were found, with powder and single crystal X-ray diffraction techniques being employed to verify their unique diffraction patterns. In the thermodynamic modelling of the SLE diagrams, two COSMO-RS parametrizations (TZVP and TZVPD-FINE) were also applied, though neither consistently delivered a better description over the other.

Abstract Herein, the conjugation of carbon dots (CDs) with TiO2 nanoparticles is reported to prepare a photocatalytic nanocomposite for an enhanced visible-light-driven photodegradation of methylene blue (MB). CDs are prepared from citric acid (CA) and ethylenediamine (EDA) via hydrothermal treatment. Using MB as a model pollutant, it is observed that, under visible-light irradiation, the nanocomposite presents an increment of the catalytic performance of 367% when compared to bare TiO2. This is achieved because the addition of CDs leads to increased visible-light absorption and hinders the recombination of photogenerated charge carriers. Thus, CDs are capable of bridging some of the limitations posed by TiO2. Tests using reactive species scavengers indicate that the main active species involved in the photodegradation by the nanocomposites are superoxide radicals followed by hydroxyl radicals, which differs from bare TiO2. Lastly, a life cycle assessment (LCA) study shows that, when accounting for performance, the nanocomposites have lower relative environmental impacts than bare TiO2. In addition, the safety of the produced CDs is shown by in vitro assays. In summary, due to conjugation with CDs, a relevant increment in the catalytic performance of TiO2 is achieved; providing an important step toward the sustainable rational design of active visible-light-driven photocatalysts.

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 PFASs are a class of highly persistent chemicals that are slowly infiltrating soils and waterways. Thus, there is a great need for fast, sensitive, and reliable techniques to detect PFASs. Conventional methods, such as LC-MS/SPE, allow high sensitivities. However, such methods can be complex and expensive. Considering this, it is not surprising that the scientific community has turned their attention to the search for alternatives. New types of PFAS sensors have been reported over the years, being generally part of three classes: optical, electrochemical, or hybrid sensors. Carbon dots (CDs) are new alternative fluorescent sensors that can present great affinity towards PFASs, while allowing for a fast response and promising sensitivity and selectivity. Furthermore, CDs have more attractive properties than traditional fluorophores and even metal-based nanomaterials that make them better candidates for sensing applications. Thus, CDs display great potential for permitting a fast and accurate quantification of PFASs. This review aims to serve as a basis for the future development and optimization of CD-based fluorescent sensors for PFASs.