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Currently, in the context of biorefinery and bioeconomy, lignocellulosic biomass is increasingly used to produce biofuels, biochemicals and other value-added products. Microwaves and ultrasound are emerging techniques that enable efficient and environmentally sustainable routes in the transformation of lignocellulosic biomass. This review presents some of the most important works published in the last few years on the application of microwaves and/or ultrasound in lignocellulosic materials pretreatment and can be used as a starting point for research into this theme. This review is divided into four parts. In Part I, the theoretical fundamentals of microwave and ultrasound treatments are reviewed. Dielectric constants for biomass, factors that influence pretreatment, are some of the subjects addressed. In Part II, the effects that these techniques have on lignocellulosic biomass (on the size and surface area of the particle; on the content of lignin, hemicellulose and cellulose; on the crystallinity index of cellulose; on the effect of solubilization of organic matter; on hydrolysis and reduction of sugars) are discussed. In Part III, emphasis is given to the contribution of microwaves and ultrasound in obtaining value-added products. In this context, several examples of liquefaction and extraction procedures are presented. Part IV describes examples of performing sonocatalysis on lignocellulosic biomass to obtain value-added products, such as furfural, whose production is significantly reduced by ultrasound treatment.

Plant sterols (PS) are cholesterol-like terpenoids widely spread in the kingdom Plantae. Being the target of extensive research for more than a century, PS have topped with evidence of having beneficial effects in healthy subjects and applications in food, cosmetic and pharmaceutical industries. However, many gaps in several fields of PS’s research still hinder their widespread practical applications. In fact, many of the mechanisms associated with PS supplementation and their health benefits are still not fully elucidated. Furthermore, compared to cholesterol data, many complex PS chemical structures still need to be fully characterized, especially in oxidized PS. On the other hand, PS molecules have also been the focus of structural modifications for applications in diverse areas, including not only the above-mentioned but also in e.g., drug delivery systems or alternative matrixes for functional foods and fats. All the identified drawbacks are also superimposed by the need of new PS sources and technologies for their isolation and purification, taking into account increased environmental and sustainability concerns. Accordingly, current and future trends in PS research warrant discussion.

Water absorption capacity is a key characteristic of cellulosic pulps used for different commodities. This property is influenced by the affinity of the pulp fiber surface with water, chemical composition of the pulp, morphology, and organization of fibers in the network. In this study, surface properties of six industrial Eucalyptus bleached kraft pulps (fluff pulps) dry-defiberized in a Hammermill, which were obtained by wood pulping and pulp bleaching under different production conditions, were studied while employing dynamic water vapor sorption and contact angles measurements. The absorption properties of air-laid pulp pads were analyzed following the absorbency testing procedure and the relationship between these properties and pulp’s chemical composition and fiber network structure were assessed by multivariate analysis. The results showed that the accessibility of the fiber surface is related to the reduction of the contact angles, but, at the same time, to the longer absorption time and less absorption capacity of the fiber network. Therefore, the absorption properties of the pulps are not necessarily directly related to their surface properties. Indeed, absorptivity is related to the surface chemical composition, fiber morphology, and fiber network structure. Thus, surface carboxylic groups promote total water uptake, resulting in better absorption capacity. Greater fiber coarseness and deformations (curl and kink) provide a less wettable surface, but a more porous network with higher specific volume, resulting in more absorbent air-laid formulations.

Rigid polyurethane foams (RPUFs) were synthesized using exclusively lignin-based polyol (LBP) obtained via the oxyalkylation of kraft lignin with propylene carbonate (PC). Using the design of experiments methodology combined with statistical analysis, the formulations were optimized to obtain a bio-based RPUF with low thermal conductivity and low apparent density to be used as a lightweight insulating material. The thermo-mechanical properties of the ensuing foams were compared with those of a commercial RPUF and a RPUF (RPUF-conv) produced using a conventional polyol. The bio-based RPUF obtained using the optimized formulation exhibited low thermal conductivity (0.0289 W/m·K), low density (33.2 kg/m3), and reasonable cell morphology. Although the bio-based RPUF has slightly lower thermo-oxidative stability and mechanical properties than RPUF-conv, it is still suitable for thermal insulation applications. In addition, the fire resistance of this bio-based foam has been improved, with its average heat release rate (HRR) reduced by 18.5% and its burn time extended by 25% compared to RPUF-conv. Overall, this bio-based RPUF has shown potential to replace petroleum-based RPUF as an insulating material. This is the first report regarding the use of 100% unpurified LBP obtained via the oxyalkylation of LignoBoost kraft lignin in the production of RPUFs.

The effects of treating industrial (laboratory-unwashed) oxygen-delignified eucalypt kraft pulp with a commercial endo-xylanase (X) on ECF bleaching performance were evaluated. Changes in fibre morphology, pulp bleachability and quality, and bleaching effluent parameters were assessed. Although no significant morphological changes were observed, fibres showed some external fibrillation. The X stage reduced both the amount and the integrity of xylans remaining in the fibres, causing their redistribution inside the cell wall. In bleaching, the X treatment allowed the reduction of ClO2 and NaOH loads by 20 and 10%, respectively. Furthermore, the brightness stability of enzyme-treated bleached pulps was improved, which was assigned to the decrease in the content of hexenuronic acid residues. The X treatment did not affect the cellulosic counterpart of pulp and did not cause a significant impact on the papermaking properties, even when xylan degradation was somewhat excessive. The enzymatic treatment caused a significant increase in the chemical oxygen demand (COD) of the respective effluent. The realistic conditions used provide a better insight into the overall impact of this technology at a pulp mill.

This study aimed to develop new rigid polyurethane foams (RPUFs) for thermal insulation based on kraft lignin, the main by-product of the pulp and paper industry. Crude lignin-based polyol (LBP) was obtained via the oxyalkylation of kraft lignin using propylene carbonate (PC). A design of experiments (DoE) was used to evaluate the effect of the isocyanate (NCO)-to-hydroxyl (OH)-group’s ratio, the content of crude LBP, the blowing agent (BA), and catalyst on the thermal conductivity and density of RPUFs. Statistical analysis revealed that the increase in crude LBP and BA content in the formulation decreases the thermal conductivity and density of the foams. In addition, the fact that LBP is a viscous polyol containing PC-oligomers appears to affect the cellular structure of RPUFs, and consequently reduces their mechanical and thermal properties. The main novelty of this study consisted in the careful optimization of the formulation, namely, with regard to the type of blowing agent and with the high content of crude LBP obtained from the oxyalkylation of LignoBoost kraft lignin without purification to obtain good quality RPUF that meets market requirements for insulation materials.

Lignin-based polyol was obtained via oxyalkylation reaction with propylene carbonate using eucalyptus kraft lignin isolated from the industrial cooking liquor by the Lignoboost® procedure. This lignin-based polyol (LBP) was used without purification in the preparation of polyurethane (PU) adhesives combined with polymeric 4,4′-methylenediphenyl diisocyanate (pMDI). A series of adhesives were obtained by varying the NCO/OH ratio of PU counterparts (pMDI and LBPs) and their performance was evaluated by gluing wood pieces under predefined conditions. The adhesion properties of the novel PU adhesive were compared with those of a commercial PU adhesive (CPA). The occurrence and extent of curing reactions and changes in the polymeric network of PA were monitored by Fourier transform infrared spectroscopy (FTIR) and dynamic mechanical analysis. Although the lap shear strength and glass transition temperature of the lignin-based PU adhesives have increased steadily with the NCO/OH ratio ranging from 1.1–2.2, chemical aging resistance can be compromised when the NCO/OH is very low. It was found that the lignin-based PU adhesive with an NCO/OH ratio of 1.3 showed better chemical resistance and adhesion efficiency than CPA possibly because the NCO/OH in the latter is too high as revealed by FTIR spectroscopy. Despite some lower thermal stability and shorter gelation time of lignin-based PU than CPA, the former revealed great potential to reduce the use of petroleum-derived polyols and isocyanates with potential application in the furniture industry as wood bonding adhesive.

All-lignin coating formulations were prepared while combining water-soluble cationic kraft lignin (quaternized LignoBoost®, CL) and anionic lignosulphonate (LS). The electrostatic attraction between positively charged CL and negatively charged LS led to the formation of insoluble self-organized macromolecule aggregates that align to films. The structures of the formed layers were evaluated by atomic force microscopy (AFM), firstly on glass lamina using dip-coating deposition and then on handsheets and industrial uncoated paper using roll-to-roll coating in a layer-by-layer mode. Coated samples were also characterized by optical microscopy, scanning electron microscopy (SEM) coupled with energy dispersive spectroscopy (SEM/EDS), and contact angle measurements. It was suggested that the structure of all-lignin aggregates is the result of the interaction of amphiphilic water-soluble lignin molecules leading to their specifically ordered mutual arrangement depending on the order and the mode of their application on the surface. The all-lignin coating of cellulosic fiber imparts lower air permeability and lower free surface energy to paper, mainly due to a decrease in surface polarity, thus promoting the paper’s hydrophobic properties. Moderate loading of lignin coating formulations (5–6 g m−2) did not affect the mechanical strength of the paper.

Currently, the pulp and paper industry generates around 50–70 million tons of lignin annually, which is mainly burned for energy recovery. Lignin, being a natural aromatic polymer rich in functional hydroxyl groups, has been drawing the interest of academia and industry for its valorization, especially for the development of polymeric materials. Among the different types of polymers that can be derived from lignin, polyurethanes (PUs) are amid the most important ones, especially due to their wide range of applications. This review encompasses available technologies to isolate lignin from pulping processes, the main approaches to convert solid lignin into a liquid polyol to produce bio-based polyurethanes, the challenges involving its characterization, and the current technology assessment. Despite the fact that PUs derived from bio-based polyols, such as lignin, are important in contributing to the circular economy, the use of isocyanate is a major environmental hot spot. Therefore, the main strategies that have been used to replace isocyanates to produce non-isocyanate polyurethanes (NIPUs) derived from lignin are also discussed.

Systemic fungal infections are associated with significant morbidity and mortality, and Candida albicans is the most common causative agent. Recognition of yeast cells by immune cell surface receptors can trigger phagocytosis of fungal pathogens and a pro-inflammatory response that may contribute to fungal elimination. Nevertheless, the elicited inflammatory response may be deleterious to the host by causing excessive tissue damage. We developed a nanoparticle-based approach to modulate the host deleterious inflammatory consequences of fungal infection by using β1,3-glucan-functionalized polystyrene (β-Glc-PS) nanoparticles. β-Glc-PS nanoparticles decreased the levels of the proinflammatory cytokines TNF-α, IL-6, IL-1β and IL-12p40 detected in in vitro culture supernatants of bone marrow-derived dendritic cells and macrophage challenged with C. albicans cells. Moreover, β-Glc-PS nanoparticles impaired the production of reactive oxygen species by bone marrow-derived dendritic cells incubated with C. albicans. This immunomodulatory effect was dependent on the nanoparticle size. Overall, β-Glc-PS nanoparticles reduced the proinflammatory response elicited by fungal cells in mononuclear phagocytes, setting the basis for a targeted therapy aimed at protecting the host by lowering the inflammatory cost of infection.

Lignosulfonates (LS) are products from the sulfite pulping process that could be applied as renewable environmentally-friendly polymeric surfactants. Being widely used as plasticizers and water-reducing admixtures in concrete formulations LS compete in the market with petroleum-based superplasticizers, such as naphthalene sulfonate formaldehyde polycondensate (NSF) and copolymer polycarboxylate ethers (PCE). In this work, different chemical modification strategies were used to improve LS performance as dispersants for concrete formulations. One strategy consisted in increasing the molecular weight of LS through different approaches, such as laccase and polyoxometalate-mediated polymerization, glyoxalation, and reversible addition-fragmentation chain transfer (RAFT) polymerization. The other strategy consisted of preparing LS-based non-ionic polymeric dispersants using two different epoxidized oligomer derivatives of poly(ethylene glycol) (PEG) and poly(propylene glycol) (PPG). Modified LS were used to prepare cement pastes, which were examined for their fluidity. Results revealed that the most promising products are PPG-modified LS due to the introduction of PPG chains by reaction with phenolic moieties in LS. The enhanced dispersant efficiency of the ensuing products is probably related not only to electrostatic repulsion caused by the sulfonic ionizable groups in LS but also to steric hindrance phenomena due to the grafted bulky PPG chains.

In this study, lignosulfonate (LS) from the acid sulfite pulping of eucalypt wood was used to synthesize LS-based polyurethanes (PUs) doped with multiwalled carbon nanotubes (MWCNTs) within the range of 0.1–1.4% w/w, yielding a unique conducting copolymer composite, which was employed as a sensitive material for all-solid-state potentiometric chemical sensors. LS-based PUs doped with 1.0% w/w MWCNTs exhibited relevant electrical conductivity suitable for sensor applications. The LS-based potentiometric sensor displayed a near-Nernstian or super-Nernstian response to a wide range of transition metals, including Cu(II), Zn(II), Cd(II), Cr(III), Cr(VI), Hg(II), and Ag(I) at pH 7 and Cr(VI) at pH 2. It also exhibited a redox response to the Fe(II)/(III) redox pair at pH 2. Unlike other lignin-based potentiometric sensors in similar composite materials, this LS-based flexible polymeric membrane did not show irreversible complexation with Hg(II). Only a weak response toward ionic liquids, [C2mim]Cl and ChCl, was registered. Unlike LS-based composites comprising MWCNTs, those doped with graphene oxide (GO), reduced GO (rGO), and graphite (Gr) did not reveal the same electrical conductivity, even with loads up to 10% (w/w), in the polymer composite. This fact is associated, at least partially, with the different filler dispersion abilities within the polymeric matrix.

Ellagitannins (ETs), characterized by their diversity and chemical complexity, belong to the class of hydrolysable tannins that, via hydrolysis under acidic or alkaline conditions, can yield ellagic acid (EA). They are mostly found as a part of extractives in angiosperms. As known antioxidants and chelators, EA and EA derivatives are drawing an increasing interest towards extensive technical and biomedical applications. The latter ones include possible antibacterial, antifungal, antiviral, anti-inflammatory, hepato- and cardioprotective, chemopreventive, neuroprotective, anti-diabetic, gastroprotective, antihyperlipidemic, and antidepressant-like activities, among others. EA’s synthesis and production challenges prompt further research on new methods and alternative sources. Conventional and prospective methods and raw materials for the production of EA and its derivatives are reviewed. Among the potential sources of EA, the residues and industrial streams of the pulp industry have been highlighted and considered as an alluring alternative in terms of commercial exploitation.

This study reports the synthesis of polyurethane–lignin copolymer blended with carbon multilayer nanotubes to be used in all-solid-state potentiometric chemical sensors. Known applicability of lignin-based polyurethanes doped with carbon nanotubes for chemical sensing was extended to eucalyptus LignoBoost® kraft lignin containing increased amounts of polyphenolic groups from concomitant tannins that were expected to impart specificity and sensitivity to the sensing material. Synthesized polymers were characterized using FT-MIR spectroscopy, electrical impedance spectroscopy, scanning electron microscopy, thermogravimetric analysis, and differential scanning calorimetry and are used for manufacturing of all solid-state potentiometric sensors. Potentiometric sensor with LignoBoost® kraft lignin-based polyurethane membrane displayed theoretical response and high selectivity to Cu (II) ions, as well as long-term stability.

The valorization of lignins as renewable aromatic feedstock is of utmost importance in terms of the use of sustainable resources. This study provides a deductive approach towards market-oriented lignin-derived antioxidants by ascertaining the direct effect of different structural features of lignin on the reactivity of its phenolic OH groups in the radical scavenging reactions. The antioxidant activity of a series of compounds, modeling lignin structural units, was experimentally characterized and rationalized, using thermodynamic descriptors. The calculated O−H bond dissociation enthalpies (BDE) of characteristic lignin subunits were used to predict the modification pathways of technical lignins. The last ones were isolated by soda delignification from different biomass sources and their oligomeric fractions were studied as a raw material for modification and production of optimized antioxidants. These were characterized in terms of chemical structure, molecular weight distribution, content of the functional groups, and the antioxidant activity. The developed approach for the targeted modification of lignins allowed the products competitive with two commercial synthetic phenolic antioxidants in both free radical scavenging and stabilization of thermooxidative destruction of polyurethane films.

Porphyra dioica is a commercial seaweed consumed all over the world, mostly in the shape of nori sheets used for “sushi” preparation. It is a well-known part of the Asian diet with health benefits, which have been associated, among others, to the high levels of n-3 and n-6 fatty acids in this red alga. However, other highly valued lipids of Porphyra are polar lipids that remain largely undescribed and can have both nutritional value and bioactivity, thus could contribute to the valorization of this seaweed. In this context, the present work aims to identify the lipidome of two life cycle stages of the Atlantic species Porphyra dioica: the early life stage conchocelis produced in an indoor-nursery, and young blades produced outdoors using an integrated multitrophic aquaculture (IMTA) framework. Both the blades (gametophyte) and conchocelis (sporophyte) are commercialized in the food and cosmetics sectors. Liquid chromatography coupled to Q–Exactive high resolution-mass spectrometry (MS) platform was used to gain insight into the lipidome of these species. Our results allowed the identification of 110 and 100 lipid molecular species in the lipidome of the blade and conchocelis, respectively. These lipid molecular species were distributed as follows (blade/conchocelis): 14/15 glycolipids (GLs), 93/79 phospholipids (PLs), and 3/6 betaine lipids. Both life stages displayed a similar profile of GLs and comprised 20:4(n-6) and 20:5(n-3) fatty acids that contribute to n-3 and n-6 fatty acid pool recorded and rank among the molecular species with higher potential bioactivity. PLs’ profile was different between the two life stages surveyed, mainly due to the number and relative abundance of molecular species. This finding suggests that differences between both life stages were more likely related with shifts in the lipids of extraplastidial membranes rather than in plastidial membranes. PLs contained n-6 and n-3 precursors and in both life stages of Porphyra dioica the n-6/n-3 ratio recorded was less than 2, highlighting the potential benefits of using these life stages in human diet to prevent chronic diseases. Atherogenic and thrombogenic indexes of blades (0.85 and 0.49, respectively) and conchocelis (0.34 and 0.30, respectively) are much lower than those reported for other Rhodophyta, which highlights their potential application as food or as functional ingredients. Overall, MS-based platforms represent a powerful tool to characterize lipid metabolism and target lipids along different life stages of algal species displaying complex life cycles (such as Porphyra dioica), contributing to their biotechnological application.