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Lignin represents a promising source of renewable energy. The development of CLEO (Cold processed Lignin Ethanol Oil) fuel introduces a novel lignin valorization approach, proposing its potential as maritime biofuel. However, its industrial success depends on enhancing fractionation yields and reducing solvent evaporation, which necessitates a detailed analysis of lignin properties, solvent types, and process parameters. By using novel combinations of biobased solvents, yields improved from 34 wt% to 49-53 wt% by using 30 wt% water or 40 wt% glycerol in ethanol, where Hildebrand Solubility Parameters emerged as indicative tool for increasing yields. Experiments on solid-to-liquid (S:L) ratios revealed a good balance between yield and lignin dispersion concentration at an S:L of 1:2.5. Producing CLEO with an improved solvent composition and S:L ratio resulted in 89 wt% yield while eliminating solvent evaporation requirements. This study highlights the potential for enhancing CLEO production efficiency and advancing it to industrial scale.
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In contrast to conventional non-biobased adsorbents, lignin emerges as a cost-effective and environmentally benign alternative for water treatment. This study identifies unexpected and unpredicted multifunctional properties of lignin nanoparticles (LNPs). LNPs, which are prepared by simple physical processes, demonstrated for the first time to behave as multifunctional materials able to adsorb and photodegrade methylene blue (MB) in aqueous medium upon UV irradiation. Furthermore, the synthetic approach adopted to synthesize LNPs - and therefore their surface properties - strongly affects their performances. More specifically, LNPs obtained by solvent-antisolvent nanoprecipitation (SLNPs) show the highest MB adsorption properties (98% removal), reaching a maximum adsorption capacity of 43 mg g-1, and the fastest adsorption kinetics with respect to other lignin-based adsorbents. Conversely, hydrotropic LNPs (HLNPs) exhibit exceptional photocatalytic activity, resulting in 98% MB degradation over 6 hours of UV irradiation, combined with the ability to be easily recycled and reused. The present effort paves the way for the use of LNPs as efficient multifunctional materials able to perform concurrently adsorption and photocatalytic degradation of dye pollutants, toward the creation of a sustainable biobased water treatment platform.
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The development of strategies allowing either the production of high value phenolics, or the isolation of properties-enhanced materials from technical lignins represents a fundamental step in the industrial upcycling of technical lignins. Both aims are met by the strategy presented in the present work, relying on the coupling of solvent-based fractionation with the oxidative action of a new type of alkaline-stable genetically modified bacterial laccase. The described approach succeeded in the tandem, high-yield and selective isolation of valuable lignin-monomeric compounds (MCs) and high molecular weight and hydrophobicity-tailored polymerised materials (PMs) from two technical lignins, namely softwood kraft lignin (SKL), and wheat straw organosolv lignin (WSL). With respect to MCs, higher yields as compared to similar studies (up to 17.2â mg/g) were achieved. PMs from SKL samples where characterised by an almost quadrupled Mw, while in the case of WSL the Mw was approximately doubled. Noteworthy, the reaction conditions were optimized in terms of reaction temperature, time, enzymatic loading, and alkalinity for the selective production of single MCs. Most interestingly, technical lignins as well as their fractions and the PMs deriving from their laccase-catalysed oxidation showed increased hydrophobicity.
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The demand for high-performance bio-based materials towards achieving more sustainable manufacturing and circular economy models is growing significantly. Kraft lignin (KL) is an abundant and highly functional aromatic/phenolic biopolymer, being the main side product of the pulp and paper industry, as well as of the more recent 2nd generation biorefineries. In this study, KL was incorporated into a glassy epoxy system based on the diglycidyl ether of bisphenol A (DGEBA) and an amine curing agent (Jeffamine D-230), being utilized as partial replacement of the curing agent and the DGEBA prepolymer or as a reactive additive. A D-230 replacement by pristine (unmodified) KL of up to 14 wt.% was achieved while KL-epoxy composites with up to 30 wt.% KL exhibited similar thermo-mechanical properties and substantially enhanced antioxidant properties compared to the neat epoxy polymer. Additionally, the effect of the KL particle size was investigated. Ball-milled kraft lignin (BMKL, 10 µm) and nano-lignin (NLH, 220 nm) were, respectively, obtained after ball milling and ultrasonication and were studied as additives in the same epoxy system. Significantly improved dispersion and thermo-mechanical properties were obtained, mainly with nano-lignin, which exhibited fully transparent lignin-epoxy composites with higher tensile strength, storage modulus and glass transition temperature, even at 30 wt.% loadings. Lastly, KL lignin was glycidylized (GKL) and utilized as a bio-based epoxy prepolymer, achieving up to 38 wt.% replacement of fossil-based DGEBA. The GKL composites exhibited improved thermo-mechanical properties and transparency. All lignins were extensively characterized using NMR, TGA, GPC, and DLS techniques to correlate and justify the epoxy polymer characterization results.
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Kraft lignin, a by-product from the production of pulp, is currently incinerated in the recovery boiler during the chemical recovery cycle, generating valuable bioenergy and recycling inorganic chemicals to the pulping process operation. Removing lignin from the black liquor or its gasification lowers the recovery boiler load enabling increased pulp production. During the past ten years, lignin separation technologies have emerged and the interest of the research community to valorize this underutilized resource has been invigorated. The aim of this Review is to give (1)â a dedicated overview of the kraft process with a focus on the lignin, (2)â an overview of applications that are being developed, and (3)â a techno-economic and life cycle asseeements of value chains from black liquor to different products. Overall, it is anticipated that this effort will inspire further work for developing and using kraft lignin as a commodity raw material for new applications undeniably promoting pivotal global sustainability concerns.
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Nowadays sustainable nanotechnological strategies to improve the efficiency of conventional agricultural practices are of utmost importance. As a matter of fact, the increasing use of productive factors in response to the growing food demand plays an important role in determining the environmental impact of agriculture. In this respect, low-efficiency conventional practices are becoming obsolete. On the other hand, the exploitation of nanoscaled systems for the controlled delivery of fertilizers, pesticides and herbicides shows great potential towards the development of sustainable, efficient and resilient agricultural processes, while promoting food security. In this context, lignin - especially in the form of its nanostructures - can play an important role as sustainable biomaterial for nano-enabled agricultural applications. In this review, we present and discuss the current advancements in the preparation of lignin nanoparticles for the controlled release of pesticides, herbicides, and fertilizers, as well as the latest findings in terms of plant response to their application. Special attention has been paid to the state-of-the-art literature concerning the release performance of these lignin-based nanomaterials, whose efficiency is compared with the conventional approaches. Finally, the major challenges and the future scenarios of lignin-based nano-enabled agriculture are considered.
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Invited for this month's cover is the work by Claudia Crestini and collaborators at Ca'Foscari University of Venice, Italy, and University of Insubria, Italy. The image shows the formation of low-molecular-weight compounds by the oxidative depolymerization of lignin by the laccase-Lig multienzymatic multistep system. The Research Article itself is available at 10.1002/cssc.202201147.
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Lacasa , Lignina , Lacasa/metabolismo , Lignina/metabolismo , Oxidación-ReducciónRESUMEN
A laccase-Lig multienzymatic multistep system for lignin depolymerization was designed and developed. Studies were performed on pristine and fractionated lignins (Kraft and Organosolv) using a specific cascade of enzymes, that is, laccases from Bacillus licheniformis and from Funalia trogii, respectively for Kraft and Organosolv lignin, followed by the Lig system from Sphingobium sp. SYK-6 (ß-etherases Ligâ E and Ligâ F, glutathione lyase Ligâ G). Careful elucidation of the structural modifications occurring in the residual lignins associated with the identification and quantification of the generated low-molecular-weight compounds showed that (i)â the laccase-Lig system cleaves non-phenolic aryl glycerol ß-O-4 aryl ether bonds, and (ii)â the overall reactivity is heavily dependent on the individual lignin structure. More specifically, samples with low phenolic/aliphatic OH groups ratio undergo net depolymerization, while an increased phenolic/aliphatic OH ratio results in the polymerization of the residual lignin irrespective of its botanical origin and isolation process.
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Lignina , Liasas , Lignina/química , Lacasa/química , Glicerol , Éteres , GlutatiónRESUMEN
The extensive use of non-degradable microplastics in a wide plethora of daily life products is causing serious pollution problems. More ecofriendly solutions are therefore urgently needed. In this context, the use of lignin, a largely available aromatic polymer, may represent a viable option. Due to the self-assembly ability of its molecules, lignin is in fact an ideal matrix for the fabrication of nanostructures. In this study, lignosulfonate microcapsules containing a limonene core were prepared and characterized in terms of their dimensions and of the physicochemical characteristics of the capsule-forming lignosulfonate molecules. The main purpose is to elucidate the key properties governing the pH-responsive behavior of the capsules to be able to achieve better control over the release kinetics of the entrapped compound(s). The results demonstrate that both the molecular weight and the concentration of sulfonate groups are the most important factors in this respect. Based on these findings, two strategies were followed to further tailor the capsules' behavior: (i) fractionation of the starting lignosulfonate by solvent extraction and (ii) introduction of a specific additive in the formulation. The first approach permitted to fabricate highly resistant capsules both in acidic, as well as in alkaline conditions, while in the second case the chemical structure of the additive, the diester diveratryl sebacate, allowed for fast kinetics of release, as values above 70% were reached after 24 h of incubation at pH 4 and pH 12.
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The brewery industry annually produces huge amounts of byproducts that represent an underutilized, yet valuable, source of biobased compounds. In this contribution, the two major beer wastes, that is, spent grains and spent yeasts, have been transformed into carbon dots (CDs) by a simple, scalable, and ecofriendly hydrothermal approach. The prepared CDs have been characterized from the chemical, morphological, and optical points of view, highlighting a high level of N-doping, because of the chemical composition of the starting material rich in proteins, photoluminescence emission centered at 420 nm, and lifetime in the range of 5.5-7.5 ns. With the aim of producing a reusable catalytic system for wastewater treatment, CDs have been entrapped into a polyvinyl alcohol matrix and tested for their dye removal ability. The results demonstrate that methylene blue can be efficiently adsorbed from water solutions into the composite hydrogel and subsequently fully degraded by UV irradiation.
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Background: Tannins have demonstrated antibacterial and antibiofilm activity, but there are still unknown aspects on how the chemical properties of tannins affect their biological properties. We are interested in understanding how to modulate the antibiofilm activity of tannins and in delineating the relationship between chemical determinants and antibiofilm activity. Materials and methods: The effect of five different naturally acquired tannins and their chemical derivatives on biofilm formation and planktonic growth of Salmonella Typhimurium, Pseudomonas aeruginosa, Escherichia coli and Staphylococcus aureus was determined in the Calgary biofilm device. Results: Most of the unmodified tannins exhibited specific antibiofilm activity against the assayed bacteria. The chemical modifications were found to alter the antibiofilm activity level and spectrum of the tannins. A positive charge introduced by derivatization with higher amounts of ammonium groups shifted the anti-biofilm spectrum toward Gram-negative bacteria, and derivatization with lower amounts of ammonium groups and acidifying derivatization shifted the spectrum toward Gram-positive bacteria. Furthermore, the quantity of phenolic OH-groups per molecule was found to have a weak impact on the anti-biofilm activity of the tannins. Conclusion: We were able to modulate the antibiofilm activity of several tannins by specific chemical modifications, providing a first approach for fine tuning of their activity and antibacterial spectrum.
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Novel valorization routes for tannins were opened by the development of a simple, straightforward, robust, and flexible approach to the selective functionalization of condensed and hydrolyzable tannins. Irrespective of the different degrees of polymerization, different commercial tannins were efficiently functionalized by the generation of an ether linkage bound to a short linker carrying the desired functional group. Functionalizations could be realized at varying degrees of technical loadings, i.e., amounts of introduced tannin-alien functionalities per number of phenolic hydroxyl groups. The same strategy was found suitable for the synthesis of polyethylene glycol-functionalized tannin copolymers. Condensed tannins functionalized with carboxylic acid moieties could be converted into a tannin-oligopeptide hybrid.
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The development of sustainable biorefinery products is confronted, among others, with the challenge of lignin and tannin valorization. These abundant, renewable aromatic biopolymers have not been widely exploited due to their inherent structural complexity and high degrees of variability and species diversity. The lack of a defined primary structure for these polyphenols is further compounded with complex chemical alterations induced during processing, eventually imparting a large variety of structural features of extreme significance for any further utilization efforts. Consequently, a protocol for the rapid, simple, and unequivocal identification and quantification of the various functional groups present in natural polyphenols, is a fundamental prerequisite for understanding and accordingly tailor their reactivity and eventual utility. Quantitative 31P NMR offers the opportunity to rapidly and reliably identify unsubstituted, o-mono substituted, and o-disubstituted phenols, aliphatic OHs, and carboxylic acid moieties in lignins and tannins with broad application potential. The methodology consists of an in situ quantitative lignin or tannin labeling procedure using a suitable 31P containing probe, followed by the acquisition of a quantitative 31P NMR spectrum in the presence of an internal standard. The high natural abundance of the 31P nucleus allows for small amounts of the sample (~30 mg) and short NMR acquisition times (~30-120 min) with well-resolved 31P signals that are highly dependent on the surrounding chemical environment of the labeled OH groups.
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Lignina , Taninos , Espectroscopía de Resonancia Magnética , Fenoles , PolifenolesRESUMEN
Microcapsules of sulfited Acacia mearnsii tannin (AmST-MCs) were generated for the first time via the sonochemical method. Their stability profile was assessed and set in the general context of tannin microcapsules (TMCs) generated under the same experimental conditions. The analytical data gathered in this work indicate an excellent stability of TMCs over time as well as under high temperature and pressure, which is a major milestone toward the meaningful applications of TMCs in industrial, pharmaceutical, and biomedical applications in which sterilization of TMCs might be a prerequisite. Active release is shown to be efficiently triggered by varying pH and/or salinity, with different profiles for TMCs from sulfited and nonsulfited species. Surfactants also affect the stability of TMCs significantly, with effects eventually amplifiable by pH and the inherent kosmotropic and chaotropic characteristics of salt components in solutions.
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Both condensed and hydrolysable tannins represent versatile natural polyphenolic structures exhibiting a broad range of activities that could be exploited in various fields including nutraceutics, cosmesis, consumer care, household and pharmaceutical applications. Various tannins are commercially available nowadays for use in such application fields. We have analysed a representative selection of commercially available condensed and hydrolysable tannins for structural features and purity. Using a combination of quantitative 31P NMR spectroscopy, HSQC measurements, MALDI-ToF analyses, gel permeation chromatography and wet chemical analysis, detailed structural characterisations and descriptions were possible, allowing for verification and falsification of claimed structural features.
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Taninos/química , Taninos Hidrolizables/química , Taninos Hidrolizables/aislamiento & purificación , Espectroscopía de Resonancia Magnética , Estructura Molecular , Espectrometría de Masa por Láser de Matriz Asistida de Ionización Desorción , Relación Estructura-Actividad , Taninos/aislamiento & purificaciónRESUMEN
Organosolv pretreatment represents one of the most promising biomass valorization strategies for renewable carbon-based products; meanwhile, there is an overall lack of holistic approach to how extraction conditions affect the suitable end-usages. In this context, lignin extracted from silver birch (Betula pendula L.) by a novel hybrid organosolv/steam-explosion treatment at varying process conditions (EtOH %; time; catalyst %) was analyzed by quantitative NMR (1H-13C HSQC; 13C NMR; 31P NMR), gel permeation chromatography, Fourier transform infrared (FT-IR), Pyr-gas chromatography-mass spectroscopy (GC/MS), and thermogravimetric analysis, and the physicochemical characteristics of the lignins were discussed regarding their potential usages. Characteristic lignin interunit bonding motifs, such as ß-O-4', ß-ß', and ß-5', were found to dominate in the extracted lignins, with their abundance varying with treatment conditions. Low-molecular-weight lignins with fairly unaltered characteristics were generated via extraction with the highest ethanol content potentially suitable for subsequent production of free phenolics. Furthermore, ß-ß' and ß-5' structures were predominant at higher acid catalyst contents and prolonged treatment times. Higher acid catalyst content led to oxidation and ethoxylation of side-chains, with the concomitant gradual disappearance of p-hydroxycinnamyl alcohol and cinnamaldehyde. This said, the increasing application of acid generated a broad set of lignin characteristics with potential applications such as antioxidants, carbon fiber, nanoparticles, and water remediation purposes.
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This Perspective describes the challenges and objectives associated to the development of new chemical technologies for the conversion of lignocellulose (non-food or waste) into chemicals and materials; it also provides an outlook on the sources, potential products, and issues to be addressed.
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The preparation of nanoparticles represents a powerful tool for lignin valorization, as it combines easy methodologies with high application potential. Different synthetic strategies and various lignin sources have been employed in the process. However, the great variability in the lignin structure prevents a direct comparison of the so far reported lignin nanoparticles (LNPs), especially as regards their physicochemical and functional properties. To this purpose, two green protocols, that is, solvent-antisolvent and hydrotropic, were optimized and used to generate LNPs from the same softwood kraft lignin. The nanomaterials were fully characterized to extrapolate structure/property relationships and reveal any differences in the mechanism of self-assembly. Furthermore, tests on methylene blue entrapment capacity and release behavior at two different pH values (2.0 and 7.4) evidenced a clear dependence on the LNPs characteristics and thus on the strategy adopted for their production.
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Lignins were fractionated in a segmented continuous flow fractionation (SCFF) approach using isocratic or gradient elution profiles of different solvent systems at various flow rates and temperatures against adjustable pressure regimes. Superior control of parameters such as temperature and pressure in combination with the possibility of freely combinable solvent gradients allowed facile fractionation and generation of industrially interesting fractions differing in molecular weight properties and/or in physicochemical properties in a process that could be fully remotely controlled for automation and performance. Scale-up of the process was possible in linear and parallel mode. Analyses of the realised fractions by standardised gel permeation chromatography and 31 Pâ NMR spectroscopy protocols showed that the SCFF of lignins delivered fractions that could be similar to conventional batch fractions, as well as novel/altered fractions available by applying overheated solvents in pressurised systems.
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Thymol and the corresponding brominated derivatives constitute important biological active molecules as antibacterial, antioxidant, antifungal, and antiparasitic agents. However, their application is often limited, because their pronounced fragrance, their poor solubility in water, and their high volatility. The encapsulation of different thymol derivatives into biocompatible lignin-microcapsules is presented as a synergy-delivering remedy. The adoption of lignosulfonate as an encapsulating material possessing relevant antioxidant activity, as well as general biocompatibility allows for the development of new materials that are suitable for the application in various fields, especially cosmesis. To this purpose, lignin microcapsules containing thymol, 4-bromothymol, 2,4-dibromothymol, and the corresponding O-methylated derivatives have been efficiently prepared through a sustainable ultrasonication procedure. Actives could be efficiently encapsulated with efficiencies of up to 50%. To evaluate the applicability of such systems for topical purposes, controlled release experiments have been performed in acetate buffer at pH 5.4, to simulate skin pH: all of the capsules show a slow release of actives, which is strongly determined by their inherent lipophilicity.