Publications

Abstract This study demonstrates the efficacy of ionic liquid (IL)-assisted vapor deposition in achieving high-quality and distinctive crystal film growth of two organic semiconductors (OSCs): a carbazole derivative (TCB) and a phenylamine derivative (TDAB). ILs with different wetting properties (short-chain [C2C1im][NTf2] and long-chain [C8C1im][NTf2]) and engineered shapes (microdroplets and coalesced film) were utilized as solvents in a vacuum. Through a meticulously designed experimental strategy, encompassing both sequential and simultaneous deposition of the IL and the OSC, this study unveils the pivotal role of ILs in shaping the crystallization behavior of the organic compound. Differential scanning calorimetry, polarized light microscopy, high-resolution scanning electron microscopy, and X-ray diffraction were employed for the films' thermal, morphological, and structural characterization. Thin films of TDAB exhibit crystallinity and a greater tendency to grow tridimensionally, forming giant pillars. However, the typical vertical growth of TDAB on solid substrates is altered when deposition occurs on surfaces coated with ILs. The IL promotes the lateral growth of nanostructures. The experimental results reveal variations in film morphology and coverage influenced by the cation alkyl chain length of the IL. In contrast to TDAB, TCB films are amorphous when thermally evaporated on solid substrates. Notably, IL-assisted vapor deposition induces the crystallization of TCB. Furthermore, TCB films deposited on coalesced IL films exhibit enhanced crystallinity and homogeneous horizontal growth, representing a significant finding in the context of thin film deposition and semiconductor device fabrication.

Abstract Bioluminescence (BL) and chemiluminescence (CL) are remarkable processes in which light is emitted due to (bio)chemical reactions. These reactions have attracted significant attention for various applications, such as biosensing, bioimaging, and biomedicine. Some of the most relevant and well-studied BL/CL systems are that of marine imidazopyrazine-based compounds, among which Coelenterazine is a prime example. Understanding the mechanisms behind efficient chemiexcitation is essential for the optimization and development of practical applications for these systems. Here, the CL of a fluorinated Coelenterazine analog was studied using experimental and theoretical approaches to obtain insight into these processes. Experimental analysis revealed that CL is more efficient under basic conditions than under acidic ones, which could be attributed to the higher relative chemiexcitation efficiency of an anionic dioxetanone intermediate over a corresponding neutral species. However, theoretical calculations indicated that the reactions of both species are similarly associated with both electron and charge transfer processes, which are typically used to explain efficiency chemiexcitation. So, neither process appears to be able to explain the relative chemiexcitation efficiencies observed. In conclusion, this study provides further insight into the mechanisms behind the chemiexcitation of imidazopyrazinone-based systems.

Abstract Micro- and nanoplastics (MNPs) are an important atmospheric aerosol constituent. However, there still needs to be a 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 streamlined, simplified methodology for sampling and fractionation is proposed.

Abstract Green carbon-based materials (GCM), i.e., carbon materials produced using renewable biomass or recycled waste, ought to be used to make processes sustainable and carbon-neutral. Carbon nanomaterials, like carbon dots and the nanobichar families, and carbon materials, like activated carbon and biochar substances, are sustainable materials with great potential to be used in different technological applications. In this review, the following four applications were selected, and the works published in the last two years (since 2022) were critically reviewed: agriculture, water treatment, energy management, and carbon dioxide reduction and sequestration. GCM improved the performance of the technological applications under revision and played an important role in the sustainability of the processes, contributing to the mitigation of climate change, by reducing emissions and increasing the sequestration of CO<inf>2</inf>eq.

Abstract The Mediterranean basin is highly susceptible to climate change, with soil salinization and the increase in average temperatures being two of the main factors affecting crop productivity in this region. Following our previous studies on describing the detrimental effects of heat and salt stress co-exposure on tomato plants, this study aimed to understand if substrate supplementation with a combination of arbuscular mycorrhizal fungi (AMF) and biochar could mitigate the negative consequences of these stresses. Upon 21 days of exposure, stressed tomato plants grown under supplemented substrates showed increased tolerance to heat (42 degrees C for 4 h/ day), salt (100 mM NaCl), and their combination, presenting increased biomass and flowering rate. The beneficial effects of AMF and biochar were associated with a better ionic balance (i.e. lower sodium accumulation and higher uptake of calcium and magnesium) and increased photosynthetic efficiency. Indeed, these plants presented higher chlorophyll content and improved CO2 assimilation rates. Biochemical data further supported that tomato plants grown with AMF and biochar were capable of efficiently modulating their defence pathways, evidenced by the accumulation of proline, ascorbate, and glutathione, coupled with a lower dependency on energy-costly enzymatic antioxidant players. In summary, the obtained data strongly point towards a beneficial role of combined AMF and biochar as sustainable tools to improve plant growth and development under a climate change scenario, where soil salinization and heat peaks often occur together.

Abstract Green carbon-based materials (GCM), i.e., carbon materials produced using renewable biomass or recycled waste, ought to be used to make processes sustainable and carbon-neutral. Carbon nanomaterials, like carbon dots and the nanobichar families, and carbon materials, like activated carbon and biochar substances, are sustainable materials with great potential to be used in different technological applications. In this review, the following four applications were selected, and the works published in the last two years (since 2022) were critically reviewed: agriculture, water treatment, energy management, and carbon dioxide reduction and sequestration. GCM improved the performance of the technological applications under revision and played an important role in the sustainability of the processes, contributing to the mitigation of climate change, by reducing emissions and increasing the sequestration of CO2eq.

Abstract The rapid evolution of Artificial Intelligence (AI) is profoundly shaping our society. Among various AI tools, ChatGPT stands out for its user-friendly nature and wide accessibility to the public. However, despite their countless potential benefits, these tools also face significant challenges, especially in sensitive areas like Education. In this publication, we conduct a prompt engineering essay with ChatGPT to understand the potential and challenges of this tool in designing new, high-quality chemistry laboratory activities. We aimed to assess its performance in proposing scientifically and pedagogically suitable protocols for chemistry laboratory activities based on the 11th-grade Portuguese curriculum. The initial exploratory essay was conducted to fine-tune the prompt, followed by the analysis of proposals for the five mandatory laboratory activities in this subject. ChatGPT demonstrates the ability to interpret and reproduce the specialized symbolic language of chemistry, effectively conceptualizing problems and laboratory activities in a clear and understandable manner for a broader audience (i.e., chemistry students). However, it is crucial to highlight the scientific-pedagogical limitations concerning the accuracy and appropriateness of the proposed laboratory activities, particularly in terms of safety and sustainability. Therefore, the use of AI in education should be approached critically and reflectively. While AI holds immense potential to transform the dynamics of teaching and learning, the role and expertise of the Chemistry teacher remain of the utmost importance to ensure the scientific and pedagogical quality of Chemistry classes.

Abstract Carbon dots (CDs) are fluorescent carbon-based nanomaterials with remarkable properties, making them more attractive than traditional fluorophores. Consequently, researchers focused on their development and application in fields such as sensing and bioimaging. One potential advantage of employing CDs is using organic waste as carbon precursors in their synthesis, providing a pathway for waste upcycling for a circular economy. However, waste-based CDs often have low fluorescence quantum yields (QY(FL)), limiting their practical applications. So, there is a need for a well-defined strategy to consistently produce waste-based CDs with appreciable QY(FL), irrespective of the starting waste material. Herein, we developed a fabrication strategy based on the hydrothermal treatment of waste materials, using citric acid as a co-carbon precursor and ethylenediamine as N-dopant. This strategy was tested with various materials, including corn stover, spent coffee grounds, cork powder, and sawdust. The results showed consistently appreciable QY(FL), reaching up to similar to 40 %. A Life Cycle Assessment (LCA) study demonstrated that producing these waste-based CDs has lower environmental impacts compared to CDs made solely from commercial reagents. Thus, we have established a framework for the environmentally friendly production of CDs by upcycling different waste materials without significant sacrifices in performance (QY(FL)).

Abstract In Portugal, Decree-Law no 102-D/2020 determines the establishment of networks for the selective collection of biowaste or the separation and recycling of biowaste at the source. The goal of this demanding is to decrease landfill deposition and ensure that, starting from 2030, landfills will not accept waste that can be recycled or recovered, such as biowaste from urban solid waste. This study determines the potential for energy generation through anaerobic digestion of biowaste collected from 14 Portuguese municipalities based on a previously published report on solutions for the separation, collection, and recycling at the source of biowaste. Assuming a population of 181,839 inhabitants and a selective collection of biowaste ranging from 11,659 to 17,808 tons by 2030, it is possible to generate up to 7.6 GWh of electricity. This electricity can meet the energy needs of up to 1650 people for a year and avoid until 1402 tons of CO2.