Kraft lignin solubility and its chemical modification in deep eutectic solvents

Lignin stands as a promising raw material to produce commodities and specialty chemicals, yet its poor solubility remains a big challenge. Recently, deep eutectic solvents (DES) have been proposed as sustainable solvents with high potential to dissolve and valorize lignin. In the present study, the ability of DES based on cholinium chloride ([Ch]Cl) combined with alcohols and carboxylic acids as hydrogen bond donors (HBDs) to dissolve kraft lignin and to change its chemical structure was examined. The influence of the chemical nature of HBDs, water content, and HBD:hydrogen bond acceptor (HBA) molar ratio on the solubility of kraft lignin in DES was studied (313.15 K). The kraft lignin solubility was enhanced by increasing both the HBD’s carbon chain length and the molar ratio, with [Ch]Cl:HEXA (1,6-hexanediol) and [Ch]Cl:MaleA (maleic acid) being the best studied solvents for kraft lignin dissolution, while the addition of water was a negative factor. The thermal treatments (393.15 K) of kraft lignin show that carboxylic acid-based DES promote chemical modifications to kraft lignin, including the disruption of several C–O covalent type bonds (e.g., β-O-4, α-O-4 and α-O-α), while alcohol-based DES were found to be nonderivatizing solvents maintaining the lignin chemical structure. These results show the versatility of DES, which, depending on their chemical nature, may offer distinct strategies for lignin valorization.publishe

A new approach for routine quantification of microplastics using Nile Red and automated software (MP-VAT)

Microplastics are widespread contaminants in the environment. However, most identification protocols rely on long and subjective visual counting, which could be improved using staining dyes. Thus, the objective of this work is to identify the best staining dye protocol and create an objective and quick automated counting software for microplastics. Tests were conducted to identify the most appropriate of eight staining dye solutions and of six wavelengths for virgin and weathered synthetic polymers, textile fibers, natural organic matter and filters. Nile Red produced the best results (without interfering in infrared spectra) rendering microplastics fluorescent at 254 nm, but with limited number of fluorescent polymers, and at 470 nm (with orange filter), with fluorescence of plastics as well as natural organic matter (requiring a digestion step). Next, a script was developed in ImageJ for the automatic quantification and characterization in shape (fiber, fragment, particle) and size of fluorescent microplastics, the Microplastics Visual Analysis Tool (MP-VAT). MP-VAT was evaluated, producing recovery rates in the range of 89.0-111.1% in spiked filters under 470 nm. Furthermore, this package is accompanied by a script that sets a scale from a known filter diameter, MP-SCALE, and a script that allows user threshold setting, MP-ACT.publishe

Fast and efficient method to evaluate the potential of eutectic solvents to dissolve lignocellulosic components

The application of eutectic solvents (ESs) in lignocellulosic biomass fractionation has been demonstrated as a promising approach to accomplish efficient and environmentally friendly biomass valorization. In general, ESs are a combination of two components, a hydrogen-bonding donor and a hydrogen-bonding acceptor, in which the melting point of the mixture is lower than that of the individual components. However, there are plenty of possible combinations to form ESs with the potential to apply in biomass processing. Therefore, the development of fast and effective screening methods to find combinations capable to dissolve the main biomass components—namely cellulose, hemicelluloses, and lignin—is highly required. An accurate and simple technique based on optical microscopy with or without polarized lenses was used in this study to quickly screen and monitor the dissolution of cellulose, xylose (a monomer of hemicelluloses), and lignin in several ESs. The dissolution of these solutes were investigated in different choline-chloride-based ESs (ChCl:UREA, ChCl:PROP, ChCl:EtGLY, ChCl:OXA, ChCl:GLY, ChCl:LAC). Small amounts of solute and solvent with temperature control were applied and the dissolution process was monitored in real time. The results obtained in this study showed that cellulose was insoluble in these ESs, while lignin and xylose were progressively dissolved.publishe

Use of biogenic sulfide for the synthesis of CuS nanocrystals and nanocomposites

During the metabolism of organic matter (CH2O), sulfate-reducing bacteria (SRB) use sulfate as the terminal electron acceptor, resulting in the production of H2S. This biologically generated sulfide, in the presence of metal ions, can be used for metal precipitation (Bhagat et al., 2004). The use of SRB in bioremediation processes, namely, in the reduction of highcontent sulfate and metal effluents, is well documented (Costa and Duarte, 2005; Garcia et al., 2001). Nevertheless, the process generates an excess of sulfide and the elimination of the sulfide in excess and disposal of the metal sulfides produced are also problems that need to be carefully addressed. Copper monosulfide (CuS) has gained considerable attention in material science due to its excellent potential in catalysis (Mallick et al., 2007), optical functionality (Liz-Marzan, 2006) and electronic functionalities (Kamat, 2002)

A new age for Quercus spp. fruits: review on nutritional and phytochemical composition and related biological activities of acorns

The current global food system must adapt to the expected growth of world population (about 9 billion individuals by 2050). This adaptation will probably include an increased consumption of edible wild foods, due to their richness in micronutrients and bioactive compounds, besides providing a cost-effective and sustainable way of improving caloric food security. A striking example of such natural matrices is the Quercus genus, which has the additional advantage of being widespread throughout the Northern Hemisphere. In a traditional sense, Quercus fruits (acorns) were mainly used in animal feeding, despite their potentially important role on the rural economy. But this preconception is changing. In fact, their nutritional value, high contents in phytochemical compounds, biological activity (such as antioxidant, anticarcinogenic, and cardioprotective properties) and use in the treatment of specific diseases (such as atherosclerosis, diabetes, or Alzheimer's disease) have raised the interest in integrating acorns into the human diet. Accordingly, this comprehensive overview was designed to provide an evidence-based review of the literature, with the objective to achieve useful conclusions regarding the nutritional properties, methodologies of extraction, identification, and characterization of a wide variety of bioactive compounds and scientifically validated bioactivities in Quercus species worldwide. The industrial by-products from acorn oil extraction or flour production are also included. Data regarding the analytical techniques, individual compounds, and their bioactivities, are organized in tables. The reported data are discussed and directions for further investigations are suggested, highlighting the use of acorns in food, nutraceutical, and pharmaceutical applications.info:eu-repo/semantics/publishedVersio

A logistics management system for a biomass-to-energy production plant storage park

This work was partially supported by the following entities: (L.J.N.) proMetheus-Research Unit on Energy, Materials and Environment for Sustainability-UIDP/05975/2020, funded by national funds through FCT-Fundacao para a Ciencia e Tecnologia; (R.G.) UNIDEMI-Research & Development Unit for Mechanical and Industrial Engineering-UIDB/00667/2020, funded by national funds through FCT-Fundacao para a Ciencia e Tecnologia; and (J.C.M.) GOVCOPP-Research Unit on Governance, Competitiveness and Public Policies-UID/CPO/04058/2019, funded by national funds through FCT-Fundacao para a Ciencia e Tecnologia.The biomass industry is growing due to the current search for greener and more sustainable alternatives to fossil energy sources. However, this industry, due to its singularity, presents several challenges and disadvantages related to the transportation of raw materials, with the large volumes that are usually involved. This project aimed to address this internal logistics situation in torrefied biomass pellets production with two different biomass storage parks, located in Portugal. The main park receives raw material coming directly from the source and stores it in large amounts as a backup and strategic storage park. The second park, with smaller dimensions, precedes the production unit and must be stocked daily. Therefore, a fleet of transport units with self-unloading cranes is required to help to unload the biomass at the main park and transport the raw material from this park to the one preceding the production unit. Thus, the main goal was to determine the dimensions of the fleet used in internal transportation operations to minimize the idle time of the transport units using a methodology already in use in the mining and quarrying industry. This methodology was analyzed and adapted to the situation presented here. The implementation of this study allows the elimination of unnecessary costs in an industry where the profit margins are low.publishersversionpublishe

An easy method for processing and identification of natural and synthetic microfibers and microplastics in indoor and outdoor air

Microplastics and microfibers can contaminate every matrix, including in the atmosphere, thus leading to incidental inhalation. However, concentrations of airborne synthetic particle in indoor and outdoor environments are not well understood due to the complexities of sampling, sample processing and identification. This work aims at producing a simple protocol to determine the concentrations of airborne microplastics and fibers. This is accomplished by removing organic matter using hydrogen peroxide (H2O2), followed by removal of mineral matter by density separation with sodium iodide (NaI). Finally, identification of fibers into synthetic or natural under the stereomicroscope can be achieved following a diagram produced by systematically observing the most common textile fibers. This method produces a recovery rate of 94.4 % for spiked samples and has been proven suitable for environmental samples. •Fibers and microplastics in air are easier to identify after carbonaceous matter removal;•No loss of microfiber is expected from the solutions used;•Recovery rates of spiked samples is 94.4 %.publishe

Identifying a quick and efficient method of removing organic matter without damaging microplastic samples

Natural organic matter may confound the detection of microplastics, requiring a removal step. However, most available protocols are long and lack information on removal efficiency and polymer degradation. Thus, we have determined the digestion efficiency (%) for a pool of organic matter (algae, driftwood, feathers, fish muscle, paraffin, palm oil) for five digestion solutions, hydrogen peroxide (H2O2), hydrogen peroxide with iron catalyst (H2O2 + Fe), potassium hydroxide (KOH), nitric acid (HNO3), and sodium dodecyl sulphate (SDS), under two temperatures (room temperature at 25 °C, 50 °C) and two periods (1, 6 h). H2O2 + Fe and KOH at 50 °C for 1 h had the highest digestion efficiencies, of 65.9% and 58.3% respectively (mostly limited by driftwood and paraffin). Further testing revealed that H2O2 + Fe is more appropriate for plant material and KOH for animal tissue. Weight loss (%), Fourier transform infrared spectrometry and carbonyl index of 9 virgin and 6 weathered polymers (polyethylene, polypropylene, polystyrene, polyethylene terephthalate, polyvinyl chloride, cellulose acetate, nylon) revealed that only identification of cellulose acetate was hindered. Filters were also tested revealing that quartz and glass fibre filters are resistant to these protocols. Thus, a digestion protocol based on H2O2 + Fe or KOH at 50 °C for 1 h may be used on microplastic samples.publishe

From chickpea and lupin as dairy alternatives

Funding text This work was supported by the FCT Project PTDC/BAA-AGR/28370/2017: “Bebida de proteína vegetal a partir de leguminosas europeias com potencial bioativo”; and also through the research unit UID/AGR/04129/2020 – LEAF.Consumption of plant based products as dairy alternatives is increasing steeply. This diet transition can only be achieved if these products keep the nutritional value and meet consumer's sensory acceptance. This work aimed to evaluate the decrease of the “beany” flavour and of raffinose, stachyose and verbascose contents in EU pulse beveragés production, and also the best lactic fermentation conditions of the beverages, towards chickpea- and lupin-based yoghurts, with rheology properties similar to the commercial soy yoghurts. The reduction of “beany” volatile compounds of chickpea and lupin beverages during processing was confirmed through GC–MS analysis. Soaking and cooking processes were effective in removing flatulence sugars with almost 48% loss from the initial content in lupin beverage. The fermentation conditions at 40 °C, 12 h and 2% (w/v) of starter concentration evidenced the best viscoelastic structure and flow properties. The lupin yoghurt-type showed a similar gel structure to commercial soy yoghurt. © 2022publishersversionpublishe

Investigating the photophysical properties and biological efficacy of BODIPY derivatives as photosensitizers in photodynamic therapy

The selectivity of photosensitizers for light activation is a key advantage in photodynamic therapy (PDT), allowing for precise targeting while sparing healthy cells. BODIPY derivatives have emerged as promising PDT candidates due to their tunable photophysical properties and versatile synthesis. Herein, we explore the photophysical characterization and the in vitro photodynamic activity of BODIPY analogues meso-substituted with an anthracene moiety and functionalized with iodine atoms or formyl group at 2,6-position. The formylated anthracene-BODIPY derivative exhibited the highest tumor suppression under irradiation, making it a potential candidate as PDT photosensitizer