Publications

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 <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.

Abstract Carbon dots (CDs) are carbon-based nanoparticles with very attractive luminescence features, which simplicity and flexibility of their fabrication can lead to an endless number of CDs with distinct properties and applications. High fluorescence quantum yields (QY(FL)) are generally a necessary feature for various applications of CDs. One commonly employed strategy to improve the fluorescence properties of CDs is heteroatom-doping using precursors containing desired heteroatoms (with focus on N-doping). In this work, we report the synthesis and systematic investigation of an array of N-doped CDs, obtained from the dry heating of solid mixtures of glucose and urea in different molar ratios with two main objectives: to study the role of stoichiometry in the optical properties and composition of CDs and to investigate the formation of possible alkaline-responsive nanoparticles and the potential of this procedure for obtaining CDs with higher synthesis yields. We have characterized the optical properties of this diverse array of glucose and urea-based CDs using both UV-Vis and fluorescence spectroscopies. In addition, we have also examined the CDs by using high-resolution transmission electron microscopy (HR-TEM) and X-Ray photoelectron (XPS) spectroscopy, as well as by assessing the thermal stability of the nanoparticles. We have found that this fabrication process generates two types of CDs, one readily soluble in water and other only soluble at basic pH. The latter was characterized by higher synthesis yields, and lower QY(FL) and thermal stability, when compared with those of the former. Furthermore, the stoichiometry of the N-dopant does not appear to be correlated with the QY(FL) of the obtained CDs. This study provides novel information that should be useful for the future rational development of CDs with higher QY(FL) and synthesis yields.

Abstract Considering the increased anthropogenic emissions of CO2 into the atmosphere, it is important to develop economic incentives for the use of CO2 capture methodologies. The conversion of CO2 into heterocyclic carbonates shows significant potential. However, there is a need for suitable organocatalysts to reach the required efficiency for these reactions. Given this, there has been an increasing focus on the development of organocatalytic systems consisting of a nucleophile and a hydrogen bond donor (HBD) so that CO2 conversion can occur in ambient conditions. In this work, we evaluated the potential of fluorescent carbon dots (CDs) as catalytic HBDs in the ring-opening reaction of epoxides, which is typically the rate-limiting step of CO2 conversion reactions into heterocyclic carbonates. The obtained results demonstrated that the CDs had a relevant catalytic effect on the studied model reaction, with a rate constant of 0.2361 +/- 0.008 h(-1), a percentage of reactant conversion of 70.8%, and a rate constant enhancement of 32.2%. These results were better than the studied alternative molecular HBDs. Thus, this study demonstrated that CDs have the potential to be used as HBDs and employed in organocatalyzed CO2 conversion into value-added products.

Abstract Dithiocarbazates comprise an important class of Schiff bases with remarkable biological applications due to the imine group present in their structure. However, full exploitation of the biological activity of 3-methyl-5-phenyl-pyrazoline-1-(S-benzyldithiocarbazate) (DTC) is limited due to its easy degradation and poor solubility in aqueous solutions. The loading of DTC into mesoporous silica nanoparticles (MSiNPs) can be an excellent strategy to improve the solubility of DTC in the aqueous medium. Therefore, the main goal of the present work was to design MSiNP-DTC and to evaluate the success of the loading process by measuring its physicochemical properties and evaluating the environmental safety of the new DTC formulation using different aquatic organisms, such as the microalgae Raphidocelis subcapitata, the macrophyte Lemna minor, and the marine bacterium Aliivibrio fischeri. DTC, MSiNP, and MSiNP-DTC concentrations ranging from 8.8 to 150 mg L-1 were tested for all the species, showing low toxicity against aquatic organisms. Loading DTC into MSiNPs caused a slight increase in the toxicity at the concentrations tested, only allowing for the estimation of the effect concentration causing a 20% reduction in bioluminescence or growth rate (EC20). Therefore, despite the potential of MSiNPs as a drug delivery system (DDS), it is of utmost importance to assess its impact on the safety of the new formulations.