Publications

Abstract As available tools for crop disease management are scarce, new, effective, and eco-friendly solutions are needed. So, this study aimed at assessing the antibacterial activity of a dried leaf Eucalyptus globulus Labill. aqueous extract (DLE) against Pseudomonas syringae pv. tomato (Pst), Xanthomonas euvesicatoria (Xeu), and Clavibacter michiganensis michiganensis (Cmm). For this, the inhibitory activity of different concentrations of DLE (0, 15, 30, 45, 60, 75, 90, 105, 120, 135, and 250 g L-1) was monitored against the type strains of Pst, Xeu, and Cmm through the obtention of their growth curves. After 48 h, results showed that the pathogen growth was strongly inhibited by DLE, with Xeu the most susceptible species (15 g L-1 MIC and IC50), followed by Pst (30 g L-1 MIC and IC50), and Cmm (45 and 35 g L-1 MIC and IC50, respectively). Additionally, using the resazurin assay, it was possible to verify that DLE considerably impaired cell viability by more than 86%, 85%, and 69% after Pst, Xeu, and Cmm were incubated with DLE concentrations equal to or higher than their MIC, respectively. However, only the treatment with DLE at 120 g L-1 did not induce any hypersensitive response in all pathogens when treated bacterial suspensions were infiltrated onto tobacco leaves. Overall, DLE can represent a great strategy for the prophylactic treatment of tomato-associated bacterial diseases or reduce the application of environmentally toxic approaches.

Abstract The solid-liquid phase behaviour of two tertiary alcohols, perfluoro-tert-butanol and tert-butanol, was studied here using experimental (ITC, DSC and density measurements) and theoretical (MD simulations) approaches. The phase diagram of the binary mixture reveals highly negative deviations from ideality at low concentrations, as well as the formation of co-crystals and is characterized by two eutectic points, a congruent melting point and a peritectic reaction corresponding to TBH : TBF stoichiometries of 2 : 1 and 1 : 1 respectively. Excess molar enthalpies and volumes were calculated, showing negative and positive deviations from ideality, respectively. The effect of acidity, stereochemical hindrance and phobic effects and how they affect intermolecular interactions in these binary mixtures is discussed, with the aim of designing and fine-tuning type V deep eutectic solvents. The results showed that the fluorination of tertiary alcohols can be used for the tuning of the mixing properties and solid-liquid phase diagrams.

Abstract This work reports a combined thermochemical experimental and computational study on 6-hydroxycoumarin. The standard (p degrees = 0.1 MPa) molar enthalpy of formation in the condensed state of this compound was derived from the standard molar energy of combustion in oxygen at T = 298.15 K, measured by combustion calorimetry. Calvet microcalorimetry was used to derive the standard molar enthalpy of sublimation. By combining these values, the standard molar enthalpy of formation in the gaseous phase, at T = 298.15 K,-(339.8 +/- 2.4) kJ.mol-1 was derived.Accurate quantum chemical calculations at the composite G3 and at the DLPNO-CCSD(T) levels of theory have also been conducted in order to characterize the energetics of all the hydroxycoumarins studied and their rad-icalar related species, allowing us to further support our experimental measurements and to adequately quantify and rationalize the antioxidant activity of these systems.

Abstract The discrepancy between the calculated (CBS-4M/Jenkins) and experimentally determined enthalpies of formation recently reported for the 2:1 salt TKX-50 raised the important question of whether the enthalpies of formation of other 2:1 C, H, N, O salts calculated using the CBS-4M/Jenkins method are reliable values. The standard (p degrees = 0.1 MPa) enthalpy of formation of crystalline guanidinium 5,5 '-azotetrazolate (GZT) (453.6 +/- 3.2 kJ/mol) was determined experimentally using static-bomb combustion calorimetry and was found to be in good agreement with the literature's values. However, using the CBS-4M/Jenkins method, the calculated enthalpy of formation of GZT was again in poor agreement with the experimentally determined value. The method we used recently to calculate the enthalpy of formation of TKX-50, based on the calculation of the heat of formation of the salt and of the corresponding neutral adduct, was then applied to GZT and provided excellent agreement with the experimentally determined value. Finally, in order to validate the findings, this method was also applied to predict the enthalpy of formation of a range of 1:1 and 2:1 salts (M+X- and (M+)2X2- salts, respectively), and the values obtained were comparable to experimentally determined values. The agreement using this approach was generally very good for both 1:1 and 2:1 salts; therefore, this approach provides a simple and reliable method which can be applied to calculate the enthalpy of formation of energetic C, H, N, O salts with much greater accuracy than the current, commonly used method.

Abstract A thermochemical study of 5-methyl-1H-benzotriazole and 5,6-dimethyl-1H-benzotriazole was carried out experimentally using calorimetric techniques and an effusion method. Parallel to that, a computational methodology was also applied. The massic energies of combustion and the enthalpies of sublimation were determined from static bomb combustion calorimetry and Knudsen mass-loss effusion method and/or high-temperature Calvet microcalorimetry, respectively. From these experimental data, the standard molar enthalpies of formation of the two benzotriazoles in the gaseous phase were derived. Additionally, the gas-phase enthalpies of formation of these benzotriazoles and other two methylated derivatives were calculated using the G3(MP2)// B3LYP level of theory. The data obtained allowed the study of the energetic effects associated with the presence of a methyl group in the benzotriazole structure and their comparison with identical effects in homocyclic molecules, namely benzene and naphthalene. The Gibbs energies of formation of the compounds in the crystalline and gaseous phases were also determined to assess their thermodynamic stability.

Abstract The thermodynamic characterization of dihydroxylammonium 5,5 '-bitetrazole-1,1 '-dioxide (TKX-50) was reinvestigated. Although TKX-50 is one of the most promising new-generation energetic materials, contradictory reports are found in the literature with regard to its solid enthalpy of formation. The standard (p degrees=10(5) Pa) molar enthalpy of formation of crystalline TKX-50, (175.3 +/- 1.9) kJ center dot mol(-1), was determined experimentally based on the measured standard massic energy of combustion, determined through static-bomb combustion calorimetry. Additionally, the standard molar enthalpy of sublimation of TKX-50, at T=298.15 K, (165.0 +/- 2.4) kJ center dot mol(-1), was derived from vapor pressure measurements determined by a Knudsen mass-loss effusion technique. Finally, different approaches were used in attempts to calculate the standard enthalpy of formation of TKX-50 in the solid state. A critical overview and assessment of the data on the enthalpy of formation of TKX-50 is also presented.

Abstract This experimental and computational study on the energetic properties of 2-methyl-, 3-methyl-, 4-methoxy- and 5-methoxy-indanones has been carried out using mostly calorimetric techniques and a suitable computational approach. The combustion and sublimation/vaporization enthalpies were determined via combustion calorimetry and Calvet microcalorimetry, respectively, allowing for the calculation of the standard molar enthalpies of formation in the gaseous phase. The enthalpy of sublimation of 5-methoxy-indanone was also derived via Knudsen effusion. Additionally, the gas-phase standard molar enthalpies of formation of these compounds were determined from high-level ab initio calculations at the G3(MP2)//B3LYP level of theory. The results obtained experimentally and through the computational approach are in good agreement. Thus, the gas-phase enthalpy of formation of 2-methylcyclopentanone was estimated with this approach. Moreover, the energetic effects associated with the presence of a methyl and methoxy group on the indanone core were analyzed, using the experimental values reported in this work. The presence of a methoxy group contributes to a decrease in the gas-phase enthalpy of formation, of about 153 kJ center dot mol(-1), whereas in the case of a methyl group, the corresponding value is c.a. 35 kJ center dot mol(-1). Finally, a quantitative analysis of the effects of delocalization of the electron density on the methyl-indanones was performed, using NBO calculations at the B3LYP/6-311+G(2df,2p) wave function.

Abstract A plasmonic nanostructure was constructed as a biorecognition element coupled to an optical sensing platform in sandwich format, targeting the hazelnut Cor a 14 allergen-encoding gene. The analytical performance of the genosensor presented a linear dynamic range between 100 amol L-1 and 1 nmol L-1 , a limit of detection (LOD) < 19.9 amol L-1 , and a sensitivity of 13.4 +/- 0.6 m.. The genosensor was successfully hybridized with hazelnut PCR products, tested with model foods, and further validated by real-time PCR. It reached a LOD <0.001% (10 mg kg(-1) ) of hazelnut in wheat material (corresponding to 1.6 mg kg(-1) of protein) and a sensitivity of 17.2 +/- 0.5 m. for a linear range of 0.001%-1%. Herein, a new genosensing approach is proposed as a highly sensitive and specific alternative tool with potential application in monitoring hazelnut as an allergenic food, protecting the health of sensitized/allergic individuals.

Abstract Waste, in particular, biowaste, can be a valuable sourceof novelcarbon materials. Renewable carbon materials, such as biomass-derivedcarbons, have gained significant attention recently as potential electrodematerials for various electrochemical devices, including batteriesand supercapacitors. The importance of renewable carbon materialsas electrodes can be attributed to their sustainability, low cost,high purity, high surface area, and tailored properties. Fish wasterecovered from the fish processing industry can be used for energyapplications and prioritizing the circular economy principles. Herein,a method is proposed to prepare a high surface area biocarbon fromglycogen extracted from mussel cooking wastewater. The biocarbon materialswere characterized using a Brunauer-Emmett-Teller surfacearea analyzer to determine the specific surface area and pore sizeand by scanning electron microscopy coupled with energy-dispersiveX-ray analysis, Raman analysis, attenuated total reflectance Fouriertransform infrared spectroscopy, X-ray diffraction, X-ray photoelectronspectroscopy, and transmission electron microscopy. The electrochemicalcharacterization was performed using a three-electrode system, utilizinga choline chloride-based deep eutectic solvent (DES) as an eco-friendlyand sustainable electrolyte. Optimal time and temperature allowedthe preparation of glycogen-based carbon materials, with a specificsurface area of 1526 m(2) g(-1), a pore volumeof 0.38 cm(3) g(-1), and an associated specificcapacitance of 657 F g(-1) at a current density of1 A g(-1), at 30 degrees C. The optimal material wasscaled up to a two-electrode supercapacitor using a DES-based solid-stateelectrolyte (SSE@DES). This prototype delivered a maximum capacitanceof 703 F g(-1) at a 1 A g(-1) of currentdensity, showing 75% capacitance retention over 1000 cycles, deliveringthe highest energy density of 0.335 W h kg(-1) andpower density of 1341 W kg(-1). Marine waste can bea sustainable source for producing nanoporous carbon materials tobe incorporated as electrode materials in energy storage devices.