Publications

Abstract Halogenated benzaldehydes possess unique chemical properties that render them valuable in pharmaceutical synthesis, pesticide formulation, and dye production. However, thorough thermodynamic data for these compounds remain scarce. This study aims to fill this knowledge gap by investigating key physical properties of several halogenated benzaldehydes, namely 4-chlorobenzaldehyde, 4-bromobenzaldehyde, 2,3-dichlorobenzaldehyde, 2,4-dichlorobenzaldehyde, and 2,6-dichlorobenzaldehyde. The physical properties determined in this study include volatility, phase transitions, and water solubility, all of which are crucial for predicting the environmental fate of these compounds. The vapor pressures of both crystalline and liquid phases were measured using a reliable static method, allowing for the determination of standard molar enthalpies, entropies, and Gibbs energies of sublimation and vaporization, as well as their triple points. The melting temperature and molar enthalpy, along with the isobaric molar heat capacity of the crystalline phase, were assessed using differential scanning calorimetry. Water solubility was evaluated at 25 degrees C through the saturation shake-flask method, complemented by ultra-violet visible spectroscopy. By combining sublimation and solubility data, additional properties such as Gibbs energies of hydration and Henry's law constants were derived. The experimental results were integrated into existing databases, enhancing the predictive models for properties including melting temperature, vapor pressure, solubility, Gibbs energy of hydration, and Henry's constant. These findings significantly improve the environmental modeling capabilities, providing valuable insights into the mobility and fate of halogenated benzaldehydes in various environmental contexts.

Abstract Food waste, due to the high quantities produced, becomes a significant environmental, economic, and social challenge worldwide. Simultaneously, the rising prevalence of chronic diseases has intensified the demand for healthier food options. A promising approach to address these issues involves the valorisation of food by-products for the development of innovative and healthier food products. Cucumis melo L., commonly consumed as a fruit, generates peels and seeds that are typically discarded. In the present study, the nutritional composition and antioxidant potential of pulp, peel, and seeds of C. melo L. (yellow and green melon) were comprehensively evaluated. The seeds were identified as a rich source of dietary fibre (39.0 and 39.7 g/100 g dw; p > 0.05) and protein (21.0 and 21.3 g/100 g dw; p > 0.05), exhibiting an appealing fatty acid profile. The peel contains high levels of dietary fibre (39.7 and 47.1 g/100 g dw; p > 0.05) and total phenolic compounds (1976 and 2212 mg GAE/100 g dw; p > 0.05), suggesting significant bioactive potential. The peels showed a high antioxidant capacity for both methods used, DPPH center dot (120 and 144 mg TE/100 g dw; p > 0.05) and FRAP (6146 and 7408 mg TE/100 g dw; p > 0.05) assays. Potassium emerged as the predominant mineral in the seeds (799 and 805 mg/100 dw; p > 0.05), while glutamic acid was the most abundant amino acid (4161 and 4327 mg/100 g dw; p > 0.05). These findings emphasise the antioxidant and nutritional properties of C. melo L. by-products, highlighting their potential for inclusion in novel food formulations. This study not only advances the understanding of C. melo L. properties but also supports the reduction of food waste and promotes sustainability within the food supply chain.

Abstract <jats:title>Abstract</jats:title> <jats:p>In Portugal, open consultations (OCs) in primary health care address urgent medical needs, constituting 40–50% of family doctor activity. Frequent attenders (FAs), often presenting nonacute issues, significantly contribute to health care overuse. This study aimed to identify factors associated with frequent OC use in a primary health care unit during 2022. A retrospective cross-sectional analysis was conducted on 4,269 adult patients, with frequent attendance defined as four or more consultations (≥90th percentile). Sociodemographic and clinical factors, including age, sex, employment, chronic conditions, and multimorbidity, were examined using binomial logistic regression. FAs (n = 570, 13.4%) accounted for 36.2% of all consultations. Significant associated variables included female sex (OR = 1.417), economic insufficiency (OR = 1.323), and multimorbidity (OR = 1.678). Conditions such as musculoskeletal (OR = 2.146), psychological (OR = 2.040), and neurological (OR = 1.550) disorders were strongly linked to frequent attendance. While FAs represent a minority of patients, their disproportionate use of OC services underscores the need for targeted interventions, such as individualized care plans and resource optimization, to balance demand and availability. These findings highlight critical areas for policy and practice to enhance health care efficiency.</jats:p>

Abstract Background and aim: Pregnancy after the age of 35 is correlated with an increased risk of impaired placentation and the development of pregnancy-associated complications. Changes in uterine redox balance seem to play a role in these settings. In this work, we hypothesized that local redox dysregulation impacts the placenta metabolic profile. Thus, we aimed to study the expression of enzymes/transporters related to nutrient uptake during reproductive aging and the effect of antioxidant supplementation. Methods: Placenta samples were collected from pregnant women aged between 22 and 41 years, and from mice of different reproductive ages (8-12 and 38-42 weeks). A subgroup of 38-42 weeks-old mice was treated with apocynin (5 mM) in the drinking water. Real-time PCR was carried out to assess gene expression, and immunohistochemistry or western blotting to assess protein expression. Results: A significant age-related decrease in the expression of glucose transporter type 1 (GLUT-1) was observed in both species. Regarding lipid metabolism, there was a strong negative and significant correlation between the gene expression of fatty-acid transporter type 4 and maternal age, in the human placenta. Perilipin isoform 2 (PLIN-2) decreased significantly with maternal age, in both models. Additionally, a significant age-related decrease in the gene expression of large neutral amino acid transporter type 4 with reproductive age was observed in the mice placenta. Supplementation with apocynin attenuated the observed alterations in GLUT-1 and PLIN-2. The observed changes suggest an age-related placenta metabolic dysfunction, likely associated with oxidative stress, that may negatively impact fetal and placental development.

Abstract In the original publication [1], there was an error in the Discussion section in Figure 3, entitled “Thermochemical cycle of the vaporization of dimer and monomer of furfurylamine”. The arrow representing (Formula presented.) was incorrectly labeled. The corrected Figure 3 is provided below: Additionally, there were errors in the Discussion section following Figure 3 in the original publication. In accordance with the revised Figure 3, the value (Formula presented.) = 24 kJ·mol−1 [30] was replaced with (Formula presented.) = −24 kJ·mol−1 [30]. Equation (5) of the original publication is related to Figure 3 and was therefore incorrect. The corrected Equation (5) is shown below: (Formula presented.) In the original publication, there was also an error in Table 5 (Discussion section), titled “Vaporization enthalpies according to Equations (4) and (5) for furfurylamine”. The values of (Formula presented.) calculated in this work for furfurylamine (dimer) were incorrect. The corrected values are now presented in the revised Table 5. The authors state that the scientific conclusions are unaffected. This correction was approved by the Academic Editor. The original publication has also been updated. © 2025 by the authors.

Abstract <jats:p>In the original publication [...]</jats:p>

Abstract <jats:p>Benzazole derivatives exhibit distinctive photophysical behavior due to excited‐state intramolecular proton transfer (ESIPT), making them promising candidates for optoelectronic applications such as organic light‐emitting diodes (OLEDs) and fluorescent sensors. Understanding their sublimation energetics, phase behavior, and emissive properties is essential for both fundamental studies and materials design. This article reports an investigation on two benzazole derivatives—2‐(2‐hydroxyphenyl)benzothiazole and 2‐(2‐hydroxyphenyl)benzoxazole (HBO)—through studies of thermal analysis, vapor pressure measurements, and fluorescence spectroscopy to establish structure–property relationships. Thermal stability and phase transitions are characterized using simultaneous thermogravimetry‐differential scanning calorimetry (TG‐DSC) and heat‐flux DSC. Vapor pressures are determined using both Knudsen effusion mass loss and mass spectrometry. The derived standard molar enthalpies of sublimation, vaporization, and fusion highlight the presence of heteroatom (S versus O) on intermolecular interactions. Solid‐state fluorescence measurements reveal strong emission in both compounds, with a large Stokes shift—consistent with ESIPT—and complex spectra attributed to solid‐state molecular packing. This comprehensive experimental strategy delivers benchmark thermodynamic and photophysical data, offering new insights into the interplay between molecular structure, thermal behavior, and fluorescence of benzazole derivatives. Such understanding is relevant for the development of advanced optoelectronic materials.</jats:p>

Abstract An experimental and computational thermochemical study is reported focus on the relationship between the energetic properties, the structural characteristics and the inherent reactivity of three thiothiadiazoles: 2-amino5-(methylthio-)-1,3,4-thiadiazole, 2-amino-5-(ethylthio-)-1,3,4-thiadiazole and 2-mercapto-5-methylthio-1,3,4thiadiazole. From the DSC measurements, the enthalpies of fusion and the respective onset temperatures were determined. The standard molar energies of combustion of the (alkylthio)-1,3,4-thiadiazoles were determined by rotating bomb combustion calorimetry. The corresponding standard molar enthalpies of sublimation, at T = 298.15 K, were derived from high-temperature Calvet microcalorimetry measurements and the study of the dependence of the compound's vapour pressures with the temperature, using the Knudsen-effusion technique. The combination of these experimental results enables the calculation of the standard molar enthalpies of formation in the gaseous state, at T = 298.15 K, which are discussed in terms of structural contributions. The latter property was also determined from high-level ab initio molecular orbital calculations at the G3(MP2)//B3LYP level of theory. The computed values are in good agreement with the experimental ones. In addition, a conformational and tautomeric study was conducted using the same approach, in order to provide insight on the amino/imino and thiol/thione tautomerism of the compounds studied. The amino form predominates in aminothiadiazoles, while the thione form prevails in mercaptothiadiazole. Moreover, the relative thermodynamic stability of each compound was also evaluated showing that in both solid and gas phases, the most stable species is the mercaptothiadiazole (in its thione form). The thermochemical results of the (alkylthio)-1,3,4-thiadiazoles show a good agreement with the NBO (natural bond orbitals) analysis results.

Abstract An extensive thermochemical study of gamma-undecanolactone and delta-undecanolactone has been developed using two complementary calorimetric techniques. The combustion energy of each compound was determined by static-bomb combustion calorimetry, and the corresponding enthalpy of vaporization was determined by high-temperature Calvet microcalorimetry, in which both properties of each compound are reported at T = 298.15 K. The standard molar enthalpy of formation in the gas phase of each lactone was derived by the combination of the experimental results. Additionally, high-level computational calculations were carried out, using composite ab initio G4 and G4(MP2) methods, as well as DFT M06-2X/6-311++G(d,p) approach, to estimate the corresponding enthalpy of formation in the gas phase. The experimental and computational results are in good agreement. The G4 and G4(MP2) methods show the best accordance with experimentally determined gas phase enthalpies of formation. The experimental results are discussed in terms of structural contributions to the energetic properties of the lactones studied, as well as to other alkylated gamma- and delta-lactones, and empirical correlations are suggested for the estimation of the standard molar enthalpies of formation, at T = 298.15 K, for other alkylated gamma- and delta-lactones, both in the liquid and gaseous phases, as well as for the respective enthalpies of vaporization. Finally, the thermochemistry of individual steps of lactone ring opening and successive decarboxylation mechanism, including the identification of transition states, was studied using the M06-2X/6-311++G(d,p) approach.

Abstract The present investigation describes the experimental evaluation of relevant physicochemical properties of five organochlorine compounds (OCs), including some that are related to their environmental mobility. The vapor pressures of (2,4′-Dichlorodiphenyl)dichloroethane (2,4′-DDD, CASN:53-19-0), 1,1-Dichloro-2,2-bis(4-chlorophenyl)ethane (4,4′-DDD, CASN:72-54-8) and 2,2-Bis(4-chlorophenyl)acetic acid (4,4′-DDA, CASN:83-05-6), as well as of the bactericide Nitrapyrin (CASN:1929-82-4) and of the rodenticide Crimidine (CASN:535-89-7) were determined at different temperatures. The Knudsen mass-loss effusion technique was employed to determine the sublimation vapor pressures of the referred compounds, apart from Crimidine. For the latter compound, a static method using a capacitance diaphragm manometer enabled the measurement of vapor pressures of both condensed (crystalline and liquid) phases. This technique was also used to measure the vapor pressures of the crystalline phase of Nitrapyrin over a larger temperature range, as well as its vaporization vapor pressures. The results of the standard molar enthalpies, entropies, and Gibbs energies of sublimation for all five compounds and of vaporization for Crimidine and Nitrapyrin, at reference temperatures, were derived. For these two compounds the phase diagram representations of the (p,T) results, in the vicinity of the triple point, were obtained. DSC analysis enabled the determination of the crystalline heat capacities of the five OCs studied and also of their temperatures and enthalpies of fusion. Gas-phase thermodynamic properties were estimated using quantum chemical calculations. The thermodynamic stability of the compounds studied was evaluated and compared in the crystalline and gaseous phases, at 298.15 K, in consideration with estimated results of the standard Gibbs energies of formation. Combined with other physical and chemical properties, the results derived from this study can be used to predict the mobility, and environmental fate of these pollutants. © 2024 Elsevier Ltd