Publications

Abstract The enthalpies of formation in the gaseous phase of methyl 3-methylanthranilate and methyl 5-methylanthranilate were determined from experimental measurements of the corresponding standard energies of combustion, obtained from combustion calorimetry, and the standard enthalpies of vaporization and sublimation, obtained from Calvet microcalorimetry and Knudsen mass-loss effusion. A computational study, using the G3(MP2)//B3LYP composite method, has also been performed for the calculation of the gas-phase standard enthalpies of formation of those two molecules at T = 298.15 K, as well as for the remaining isomers, methyl 4-methylanthranilate and methyl 6-methylanthranilate. The results have been used to evaluate and analyze the energetic effect of the methyl substituent in different positions of the ring.

Abstract Chemiluminescence is a remarkable process in which light is emitted due to a chemical reaction, without the need for photoexcitation. Among some of the most well-known chemiluminescent systems is that of marine Coelenterazine. Herein, we report the synthesis of a novel halogenated Coelenterazine analog, as well as the characterization of its potential anticancer activity and chemiluminescence. We have found that this analog is capable of significantly enhanced emission in aqueous solution when triggered by superoxide anion while being compatible with human cell lines. So, this compound presents great potential for the sensitive and dynamic sensing of a molecule of interest in biological media. Furthermore, the analysis of its cytotoxicity provided structural insight into the properties of brominated Coelenterazines, which were previously found to possess selective anticancer activity. Namely, the introduction of bromine heteroatoms is not enough to provide cyto-toxicity, while the introduction of electro-withdrawing groups eliminates all previously reported anticancer activity. Finally, while this compound is not active, its use in a combination approach allowed to improve the profile of a known chemotherapeutic agent. These results should be useful to guide future optimizations of halogenated Coelenterazine analogs.

Abstract Carbon dots (CDs) have attracted considerable interest from the scientific community due to their exceptional properties, such as high photoluminescence, broadband absorption, low toxicity, water solubility and (photo)chemical stability. As a result, they have been applied in several fields, such as sensing, bioimaging, artificial lighting and catalysis. In particular, CDs may act as sole photocatalysts or as part of photocatalytic nanocomposites. This study aims to provide a comprehensive review on the use of CDs as sole photocatalysts in the areas of hydrogen production via water splitting, photodegradation of organic pollutants and photoreduction and metal removal from wastewaters. Furthermore, key limitations preventing a wider use of CDs as photocatalysts are pointed out. It is our hope that this review will serve as a basis on which researchers may find useful information to develop sustainable methodologies for the synthesis and use of photocatalytic CDs.

Abstract Microalgae cultivation can be used to increase the sustainability of carbon emitting processes, converting the CO2 from exhaust gases into fuels, food and chemicals. Many of the carbon emitting industries operate in a continuous manner, for periods that can span days or months, resulting in a continuous stream of gas emissions. Biogenic CO2 from industrial microbiological processes is one example, since in many cases it becomes unsustainable to stop these processes on a daily or weekly basis. To correctly sequester these emissions, microalgae systems must be operated under continuous constant conditions, requiring photobioreactors (PBRs) that can act as chemostats for long periods of time. However, in order to optimize culture parameters or study metabolic responses, bench -scale setups are necessary. Currently there is a lack of studies and design alternatives using chemostat, since most works focus on batch assays or semi-continuous cultures. Therefore, this work focused on the development of a continuous bench-scale PBR, which combines a retention vessel, a photocollector and a degasser, with an innovative recirculation system, that allows it to operate as an autotrophic chemostat, to study carbon seques-tration from a biogenic CO2-rich constant air stream. To assess its applicability, the PBR was used to cultivate the green microalga Haematococcus pluvialis using as sole carbon source the CO2 produced by a coupled heterotro-phic bacterial chemostat. An air stream containing approximate to 0.35 vol% of CO2, was fed to the system, and it was evaluated in terms of stability, carbon fixation and biomass productivity, for dilution rates ranging from 0.1 to 0.5 d-1. The PBR was able to operate under chemostat conditions for more than 100 days, producing a stable culture that generated proportional responses to the stimuli it was subjected to, attaining a maximum biomass productivity of 183 mg/L/d with a carbon fixation efficiency of approximate to 39% at 0.3 d-1. These results reinforce the effectiveness of the developed PBR system, making it suitable for laboratory-scale studies of continuous photoautotrophic microalgae cultivation.

Abstract Microalgae represent a promising solution in addressing the impacts associated with the current agricultural and manufacturing practices which are causing irreparable environmental damage. Microalgae have considerable biosynthetic potential, being a rich source of lipids, proteins, and high-value compounds. Under the scope of the H2020-BBI MULTI-STR3AM project, an innovative large-scale production system of valuable commodities for the food, feed, and fragrance sectors is being developed on the basis of microalgae, reducing costs, increasing the scale of production, and boosting value chain sustainability. In this work, we aimed to create a process model that can mimic an industrial plant to estimate mass and energy balances, optimize scheduling, and calculate production costs for a large-scale plant. Three autotrophic microalgae strains (Nannochloropsis sp., Dunaliella sp. and Spirulina sp.) were considered for this assessment, as well as the use of locally sourced CO2 (flue gas). The developed process model is a useful tool for obtaining the data required for techno-economic analysis (TEA) and life cycle assessment (LCA) of industrial biorefinery-based processes. Nannochloropsis sp. was the most economic option, whereas Dunaliella sp. was the most expensive strain to produce due to its lower productivity. Preliminary environmental assessments of the climate change impact category revealed that water recirculation and the use of flue gas could lead to values of 5.6, 10.6, and 9.2 kgCO(2eq)center dot kg(AFDW)(-1) for Nannochloropsis sp., Dunaliella sp., and Spirulina sp., respectively, with electricity and NaCl as the main contributors. The obtained data allow for the quantification of the production costs and environmental impacts of the microalgal biomass fractions produced, which will be fundamental for future comparison studies and in determining if they are higher or lower than those of the replaced products. The process model developed in this work provides a useful tool for the evaluation and optimization of large-scale microalgae production systems.

Abstract <jats:p>Micro-nano-plastics (MNPs) are an important constituent of atmospheric aerosol. However, there is still no standard procedure for their sampling and size fractionation, which is an obstacle to the aggregation and critical analysis of results obtained by different research groups. This review focuses on the sampling and fractionation methodologies used for MNPs. Moreover, a straightforward optimized methodology for the sampling and fractionation is proposed.</jats:p>

Abstract Reactive oxygen species (ROS), including superoxide anion, are involved in regulating various signaling pathways and are also responsible for oxidative stress. Sensing superoxide anion is of particular importance due to its biological significance. One potential approach is to use Coelenterazine as a chemiluminescent probe for the dynamic sensing of this ROS. In this study, we investigated the superoxide anion-triggered chemiluminescence of native Coelenterazine and two halogenated analogs and found that they showed a similar to 100-fold enhancement of light emission in aqueous solution, which was significantly reduced in methanol and nonexistent in aprotic solvents. In fact, Coelenterazine showed more intense light emission in aprotic solvents and, interestingly, although the light emission of the analogs seemed relatively unaffected by the solvents, their chemiluminescence was significantly quenched in water compared to methanol and, especially, to aprotic media. This suggests that the quenching effect observed for Coelenterazine is responsible for the differences in aqueous media, rather than an intrinsic enhanced emission by the analogs. In summary, we present Coelenterazine analogs that could serve as a basis for enhanced sensing of superoxide anion, providing information that could further our understanding of this chemiluminescent system.

Abstract Biodesulfurization is a biotechnological process that employs microorganisms as biocatalysts to remove sulfur from fuels usually at mesophilic conditions, targeting recalcitrant organosulfur compounds without affecting their hydrocarbon structure. One of the bottlenecks hindering its large-scale application is the inhibition of biodesulfurization activity by easily metabolized sulfur compounds, such as sulfates, even at residual concentrations. This increases production costs by requiring high-purity sulfur-free nutrients or complex induction steps to prevent/revert inhibition. The objective of this work was to bypass this limitation and demonstrate that it is possible to produce biocatalysts with biodesulfurization activity using sulfate as the only sulfur source, without employing inducers or genetic manipulation, simply by adjusting the sulfur : carbon ratio in continuous culture. With this goal, the bacterium Gordonia alkanivorans strain 1B was cultivated in a chemostat with a medium containing 10 g L-1 of fructose as the carbon source and different sulfate concentrations (12-50 mg per L SO42-) using Na2SO4. Then the bacteria were employed as biocatalysts in biodesulfurization assays with a recalcitrant organosulfur compound (dibenzothiophene). Under these conditions it was observed that 2.2 mg(sulfate) g(fructose)(-1) ensured a biodesulfurization activity of 6.1 & mu;mol g(DCW)(-1) h(-1), 15% greater than previously reported for this strain with an inducer, without limiting biocatalyst production. This novel procedure was further applied to another biocatalyst, Rhodococcus erythropolis strain D1, validating its wide applicability to other desulfurizing microorganisms. Overall, these results indicate a previously unknown regulation mechanism dependent on relative sulfur concentration, which influences cellular responses and regulates biodesulfurization activity, allowing the use of easily metabolized sulfur sources to produce cost-effective biocatalysts for biodesulfurization.

Abstract <jats:p>Keywords: Wood residuals; Forest biomass; Wood composite; Wood floor; Life Cycle Assessment.</jats:p>

Abstract The effectiveness of various transition metal phosphate-based acid catalysts, including vanadium and niobium, in the hydrothermal synthesis of carbon dots (CDs), has been assessed. Two sources of carbohydrates were employed for this: commercial xylose and liquor of xylose produced by processing olive pits. Catalysts were identified using the NH3-TPD, DTA/TG, XRD, and XPS techniques. The reaction was conducted for 4 h at a temperature of 180 degrees C. The existence of such nanoparticles, regardless of the carbohydrate source, was confirmed by an analysis of the features and characteristics of CDs nanoparticles. N-doped CDs with increased fluorescence were also created at the same time using a similar hydrothermal technique, and their photocatalytic activity was investigated. A Life Cycle Assessment (LCA) was conducted for both syntheses with the goal of comparing the environmental effects of the synthesis from commercial xylose to the synthesis from biomass. It was revealed that, although energy is the primary driver of both synthesis pathways' effect categories, the fundamental variations that seem to determine their relative sustainability are connected to the nature of the carbon precursor. Regarding the latter, it is determined that electricity has the greatest environmental impact.