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Polyelectrolyte complexes (PECs) are polymeric structures formed by the self-assembly of oppositely charged polymers. Novel biomaterials based on PECs are currently under investigation as drug delivery systems, among other applications. This strategy leverages the ability of PECs to entrap drugs under mild conditions and control their release. In this study, we combined a novel and sustainably produced hemicellulose-rich lignosulphonate polymer (EH, negatively charged) with polyethyleneimine (PEI) or chitosan (CH, positively charged) and agar for the development of drug-releasing PECs. A preliminary screening demonstrated the effect of several parameters (polyelectrolyte ratio, temperature, and type of polycation) on PECs formation. From this, selected formulations were further characterized in terms of thermal properties, surface morphology at the microscale, stability, and ability to load and release methylene blue (MB) as a model drug. EH/PEI complexes had a more pronounced gel-like behaviour compared to the EH/CH complexes. Differential scanning calorimetry (DSC) results supported the establishment of polymeric interactions during complexation. Overall, PECs' stability was positively affected by low pH, ratios close to 1:1, and the addition of agar. PECs with higher EH content showed a higher MB loading, likely promoted by stronger electrostatic interactions. The EH/CH formulation enriched with agar showed the best sustained release profile of MB during the first 30 h in a pH-dependent environment simulating the gastrointestinal tract. Overall, we defined the conditions to formulate novel PECs based on a sustainable hemicellulose-rich lignosulphonate for potential applications in drug delivery, which promotes the valuable synergy between sustainability and the biomedical field.
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The inherent colloidal dispersity (due to length, aspect ratio, surface charge heterogeneity) of CNCs, when produced using the typical traditional sulfuric acid hydrolysis route, presents a great challenge when interpreting colloidal properties and linking the CNC film nanostructure to the helicoidal self-assembly mechanism during drying. Indeed, further improvement of this CNC preparation route is required to yield films with better control over the CNC pitch and optical properties. Here we present a modified CNC-preparation protocol, by fractionating and harvesting CNCs with different average surface charges, rod lengths, aspect ratios, already during the centrifugation steps after hydrolysis. This enables faster CNC fractionation, because it is performed in a high ionic strength aqueous medium. By comparing dry films from the three CNC fractions, discrepancies in the CNC self-assembly and structural colors were clearly observed. Conclusively, we demonstrate a fast protocol to harvest different populations of CNCs, that enable tailored refinement of structural colors in CNC films.
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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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Interaction between xylan and cellulose microfibrils is required to maintain the integrity of secondary cell walls. However, the mechanisms governing their assembly and the effects on cellulose surface polymers are not fully clear. Here, molecular dynamics simulations are used to study xylan adsorption onto hydrated cellulose fibrils. Based on multiple spontaneous adsorption simulations it is shown that an antiparallel orientation is thermodynamically preferred over a parallel one, and that adsorption is accompanied by the formation of regular but orientation-dependent hydrogen bond patterns. Furthermore, xylan adsorption restricts the local dynamics of the adjacent glucose residues in the surface layer to a level of the crystalline core, which is manifested as a three-fold increase in their 13C NMR T1 relaxation time. These results suggest that xylan forms a rigid and ordered layer around the cellulose fibril that functions as a transition phase to more flexible and disordered polysaccharide and lignin domains.
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Biomass electro-oxidation is a promising approach for the sustainable generation of H2 by electrolysis with simultaneous synthesis of value-added chemicals. In this work, the electro-oxidation of two structurally different organic hydroxyacids, lactic acid and gluconic acid, was studied comparatively to understand how the chemical structure of the hydroxyacid affects the electrochemical reactivity under various conditions. It was concluded that hydroxyacids such as gluconic acid, with a considerable density of C-OH groups, are highly reactive and promising for the sustainable generation of H2 by electrolysis at low potentials and high conversion rates (less than -0.15â V vs. Hg/HgO at 400â mA cm-2 ) but with low selectivity to specific final products. In contrast, the lower reactivity of lactic acid did not enable H2 generation at very high conversion rates (<100â mA cm-2 ), but the reaction was significantly more selective (64 % to pyruvic acid). This work shows the potential of biomass-based organic hydroxyacids for sustainable generation of H2 and highlights the importance of the chemical structure on the reactivity and selectivity of the electro-oxidation reactions.
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Hemicelluloses, a family of heterogeneous polysaccharides with complex molecular structures, constitute a fundamental component of lignocellulosic biomass. However, the contribution of each hemicellulose type to the mechanical properties of secondary plant cell walls remains elusive. Here we homogeneously incorporate different combinations of extracted and purified hemicelluloses (xylans and glucomannans) from softwood and hardwood species into self-assembled networks during cellulose biosynthesis in a bacterial model, without altering the morphology and the crystallinity of the cellulose bundles. These composite hydrogels can be therefore envisioned as models of secondary plant cell walls prior to lignification. The incorporated hemicelluloses exhibit both a rigid phase having close interactions with cellulose, together with a flexible phase contributing to the multiscale architecture of the bacterial cellulose hydrogels. The wood hemicelluloses exhibit distinct biomechanical contributions, with glucomannans increasing the elastic modulus in compression, and xylans contributing to a dramatic increase of the elongation at break under tension. These diverging effects cannot be explained solely from the nature of their direct interactions with cellulose, but can be related to the distinct molecular structure of wood xylans and mannans, the multiphase architecture of the hydrogels and the aggregative effects amongst hemicellulose-coated fibrils. Our study contributes to understanding the specific roles of wood xylans and glucomannans in the biomechanical integrity of secondary cell walls in tension and compression and has significance for the development of lignocellulosic materials with controlled assembly and tailored mechanical properties.
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Parede Celular/química , Celulose/química , Extratos Vegetais/química , Plantas/química , Polissacarídeos/química , Madeira/química , Configuração de Carboidratos , Sequência de Carboidratos , Catárticos/química , Citoesqueleto/química , Hidrogéis/química , Mananas , Xilanos/químicaRESUMO
A novel method exploiting the in situ reactivation of a PdNi catalyst to enhance the electro-oxidation of alcohols is reported. The periodic regeneration of the catalyst surface leads to significant gains in terms of conversion rate, energy requirements and stability compared to the conventional potentiostatic method.
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A series of optically transparent composites were made by using tunicate cellulose membranes, in which the naturally organized cellulose microfibrillar network structure of tunicate tunics was preserved and used as the template and a solution of glycerol and citric acid at different molar ratios was used as the matrix. Polymerization through ester bond formation occurred at elevated temperatures without any catalyst, and water was released as the only byproduct. The obtained composites had a uniform and dense structure. Thus, the produced glycerol citrate polyester improved the transparency of the tunicate cellulose membrane while the cellulose membrane provided rigidity and strength to the prepared composite. The interaction between cellulose and polyester afforded the composites high thermal stability. Additionally, the composites were optically transparent and their shape, strength, and flexibility were adjustable by varying the formulation and reaction conditions. These composites of cellulose, glycerol, and citric acid are renewable and biocompatible and have many potential applications as structural materials in packaging, flexible displays, and solar cells.
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Xylan is tightly associated with cellulose and lignin in secondary plant cell walls, contributing to its rigidity and structural integrity in vascular plants. However, the molecular features and the nanoscale forces that control the interactions among cellulose microfibrils, hemicelluloses, and lignin are still not well understood. Here, we combine comprehensive mass spectrometric glycan sequencing and molecular dynamics simulations to elucidate the substitution pattern in softwood xylans and to investigate the effect of distinct intramolecular motifs on xylan conformation and on the interaction with cellulose surfaces in Norway spruce (Picea abies). We confirm the presence of motifs with evenly spaced glycosyl decorations on the xylan backbone, together with minor motifs with consecutive glucuronation. These domains are differently enriched in xylan fractions extracted by alkali and subcritical water, which indicates their preferential positioning in the secondary plant cell wall ultrastructure. The flexibility of the 3-fold screw conformation of xylan in solution is enhanced by the presence of arabinofuranosyl decorations. Additionally, molecular dynamic simulations suggest that the glycosyl substitutions in xylan are not only sterically tolerated by the cellulose surfaces but that they increase the affinity for cellulose and favor the stabilization of the 2-fold screw conformation. This effect is more significant for the hydrophobic surface compared with the hydrophilic ones, which demonstrates the importance of nonpolar driving forces on the structural integrity of secondary plant cell walls. These novel molecular insights contribute to an improved understanding of the supramolecular architecture of plant secondary cell walls and have fundamental implications for overcoming lignocellulose recalcitrance and for the design of advanced wood-based materials.
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Celulose/química , Picea/química , Xilanos/química , Configuração de Carboidratos , Madeira/química , Madeira/citologiaRESUMO
This work reveals the structural variations of cellulose nanofibers (CNF) prepared from different cellulose sources, including softwood (Picea abies), hardwood (Eucalyptus grandis × E. urophylla), and tunicate (Ciona intestinalis), using different preparation processes and their correlations to the formation and performance of the films prepared from the CNF. Here, the CNF are prepared from wood chemical pulps and tunicate isolated cellulose by an identical homogenization treatment subsequent to either an enzymatic hydrolysis or a 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO)-mediated oxidation. They show a large structural diversity in terms of chemical, morphological, and crystalline structure. Among others, the tunicate CNF consist of purer cellulose and have a degree of polymerization higher than that of wood CNF. Introduction of surface charges via the TEMPO-mediated oxidation is found to have significant impacts on the structure, morphology, optical, mechanical, thermal, and hydrophobic properties of the prepared films. For example, the film density is closely related to the charge density of the used CNF, and the tensile stress of the films is correlated to the crystallinity index of the CNF. In turn, the CNF structure is determined by the cellulose sources and the preparation processes. This study provides useful information and knowledge for understanding the importance of the raw material for the quality of CNF for various types of applications.
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The macromolecular conformation of the constituent polysaccharides in lignocellulosic biomass influences their supramolecular interactions, and therefore their function in plants and their performance in technical products. The flexibility of glycosidic linkages from the backbone of hemicelluloses was studied by evaluating the conformational freedom of the φ and ψ dihedral angles using molecular dynamic simulations, additionally selected molecules were correlated with experimental data by nuclear magnetic resonance spectroscopy. Three types of ß-(1â4) glycosidic linkages involving the monosaccharides (Glcp, Xylp and Manp) present in the backbone of hemicelluloses were defined. Different di- and tetrasaccharides with combinations of such sugar monomers from hemicelluloses were simulated, and free energy maps of the φ - ψ space and hydrogen-bonding patterns were obtained. The glycosidic linkage between Glc-Glc or Glc-Man (C-type) was the stiffest with mainly one probable conformation; the linkage from Man-Man or Man-Glc (M-type) was similar but with an increased probability for an alternative conformation making it more flexible, and the linkage between two Xyl-units (X-type) was the most flexible with two almost equally populated conformations. Glycosidic linkages of the same type showed essentially the same conformational space in both disaccharides and in the central region of tetrasaccharides. Different probabilities of glycosidic linkage conformations in the backbone of hemicelluloses can be directly estimated from the free energy maps, which to a large degree affect the overall macromolecular conformations of these polymers. The information gained contributes to an increased understanding of the function of hemicelluloses both in the cell wall and in technical products.
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Simulação de Dinâmica Molecular , Polissacarídeos/química , Glucanos/química , Espectroscopia de Ressonância Magnética , Mananas/química , Estrutura Molecular , Xilanos/químicaRESUMO
With the arising of global climate change and resource shortage, in recent years, increased attention has been paid to environmentally friendly materials. Trees are sustainable and renewable materials, which give us shelter and oxygen and remove carbon dioxide from the atmosphere. Trees are a primary resource that human society depends upon every day, for example, homes, heating, furniture, and aircraft. Wood from trees gives us paper, cardboard, and medical supplies, thus impacting our homes, school, work, and play. All of the above-mentioned applications have been well developed over the past thousands of years. However, trees and wood have much more to offer us as advanced materials, impacting emerging high-tech fields, such as bioengineering, flexible electronics, and clean energy. Wood naturally has a hierarchical structure, composed of well-oriented microfibers and tracheids for water, ion, and oxygen transportation during metabolism. At higher magnification, the walls of fiber cells have an interesting morphology-a distinctly mesoporous structure. Moreover, the walls of fiber cells are composed of thousands of fibers (or macrofibrils) oriented in a similar angle. Nanofibrils and nanocrystals can be further liberated from macrofibrils by mechanical, chemical, and enzymatic methods. The obtained nanocellulose has unique optical, mechanical, and barrier properties and is an excellent candidate for chemical modification and reconfiguration. Wood is naturally a composite material, comprised of cellulose, hemicellulose, and lignin. Wood is sustainable, earth abundant, strong, biodegradable, biocompatible, and chemically accessible for modification; more importantly, multiscale natural fibers from wood have unique optical properties applicable to different kinds of optoelectronics and photonic devices. Today, the materials derived from wood are ready to be explored for applications in new technology areas, such as electronics, biomedical devices, and energy. The goal of this study is to review the fundamental structures and chemistries of wood and wood-derived materials, which are essential for a wide range of existing and new enabling technologies. The scope of the review covers multiscale materials and assemblies of cellulose, hemicellulose, and lignin as well as other biomaterials derived from wood, in regard to their major emerging applications. Structure-properties-application relationships will be investigated in detail. Understanding the fundamental properties of these structures is crucial for designing and manufacturing products for emerging applications. Today, a more holistic understanding of the interplay between the structure, chemistry, and performance of wood and wood-derived materials is advancing historical applications of these materials. This new level of understanding also enables a myriad of new and exciting applications, which motivate this review. There are excellent reviews already on the classical topic of woody materials, and some recent reviews also cover new understanding of these materials as well as potential applications. This review will focus on the uniqueness of woody materials for three critical applications: green electronics, biological devices, and energy storage and bioenergy.
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Técnicas Biossensoriais/instrumentação , Técnicas Eletroquímicas/instrumentação , Química Verde , Madeira/química , Celulose/química , Equipamentos e Provisões Elétricas , Hidrogéis , Dispositivos Lab-On-A-Chip , Lignina/química , Membranas Artificiais , Nanofibras/química , Papel , Polissacarídeos/química , Porosidade , Energia RenovávelRESUMO
The fungus Phoma herbarum isolated from soil showed growth on highly pure lignin extracted from spruce wood and on synthetic lignin (DHP). The lignin remaining after cultivation was shown to have a lower molecular weight. The reduction in the numbers of ether linkages of the extracted lignins was also observed by derivatization followed by reductive cleavage (DFRC) in combination with (31)P NMR studies. The fungal strain showed an ability to degrade synthetic lignin by extracellular catalysts. GC-MS was applied to study the evolution of low molar mass adducts, e.g., monolignols and it was shown that a reduced coniferyl alcohol product was produced from DHP in a cell-free environment. The work has demonstrated the ability of soil microbes to grow on lignin as sole carbon source. The potential impact is in the production of low molar mass renewable phenols for material application.
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Ascomicetos/metabolismo , Lignina/metabolismo , Ascomicetos/crescimento & desenvolvimento , Ascomicetos/isolamento & purificação , Carbono/metabolismo , Microbiologia do SoloRESUMO
In this study, new wood-inspired films were developed from microfibrillated cellulose and galactoglucomannan-lignin networks isolated from chemothermomechanical pulping side streams and cross-linked using laccase enzymes. To the best of our knowledge, this is the first time that cross-linked galactoglucomannan-lignin networks have been used for the potential development of composite films inspired by woody-cell wall formation. Their capability as polymeric matrices was assessed based on thermal, structural, mechanical and oxygen permeability analyses. The addition of different amounts of microfibrillated cellulose as a reinforcing agent and glycerol as a plasticizer on the film performances was evaluated. In general, an increase in microfibrillated cellulose resulted in a film with better thermal, mechanical and oxygen barrier performance. However, the presence of glycerol decreased the thermal stability, stiffness and oxygen barrier properties of the films but improved their elongation. Therefore, depending on the application, the film properties can be tailored by adjusting the amounts of reinforcing agent and plasticizer in the film formulation.
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Materiais Biomiméticos/química , Celulose/química , Mananas/química , Fenômenos Mecânicos , Oxigênio/química , Temperatura , Embalagem de Alimentos , Glicerol/química , Lignina/química , Resistência à TraçãoRESUMO
In this study we were mirroring suggested in vivo phenomena of lignin-hemicellulose complex formation in vitro, by cross-linking Norway spruce (Picea abies) galactoglucomannans, xylans and lignin moieties to high molecular weight complexes by laccase treatment. We were able to observe the oxidation and cross-linking of non-condensed guaiacyl-type phenolic moieties attached to both of the hemicelluloses by (31)P NMR and size-exclusion chromatography. We suggest that hemicelluloses-lignin complexes form covalently linked structural units during the early stages of lignification via radical enzymatic cross-linking catalyzed by laccase. This work shows that the hemicellulose molecules in wood are covalently linked to two or more lignin units thereby making them suited for forming network structures.
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Lignina/metabolismo , Mananas/metabolismo , Picea/química , Lacase/metabolismo , Lignina/análise , Lignina/química , Mananas/análise , Mananas/química , Estrutura Molecular , Noruega , Ressonância Magnética Nuclear Biomolecular , Oxirredução , Picea/metabolismo , Polissacarídeos/isolamento & purificação , Polissacarídeos/metabolismoRESUMO
A novel mechanical pre-treatment method was used to separate the wood chips into fiber bundles in order to extract high molecular weight wood polymers. The mechanical pre-treatment involved chip compression in a conical plug-screw followed by defibration in a fiberizer. The fiberized wood was treated with hot water at various combinations of time and temperature in order to analyze the extraction yield of hemicelluloses at different conditions. Nearly 6 mg/g wood of galactoglucomannan was obtained at 90 °C/120 min which was about three times more than what could be extracted from wood chips. The extracted carbohydrates had molecular weight ranging up to 60 kDa. About 10% of each of the extracted material had a molecular weight above 30 kDa. The extraction liquor could also be reused for consecutive extractions with successive increase in the extraction yield of hemicelluloses.
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Hemicelluloses are one of the main constituents of plant cell walls and thereby one of the most abundant biopolymers on earth. They can be obtained as by-products from different wood based processes, most importantly from the mechanical pulping. Hemicelluloses have interesting properties in e.g. barrier film applications. However, their relatively low molecular weight after isolation and co-extraction with lignin has limited their use. In this work, we present a novel technique for increasing the molecular weight of different wood hemicelluloses from mechanical pulping process waters as well as from pre-hydrolysis extracts. This is achieved by enzyme-catalyzed cross-linking of aromatic moieties bound to the hemicelluloses. The cross-linking treatment resulted in significantly improved mechanical properties in barrier films made with spruce galactoglucomannan. To our knowledge, this is the first time that wood hemicelluloses have been cross-linked by utilizing the bound aromatic moieties and creates new possibilities for utilizing this raw material source.
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Lacase/química , Mananas/química , Reagentes de Ligações Cruzadas/química , Lignina/química , Peso Molecular , Picea/química , Polímeros/síntese química , Polímeros/químicaRESUMO
Lignosulfonates are by-products from the sulfite pulping process. During this process, lignin is liberated from pulp fibers through sulfonation and washed away. As a consequence, the lignosulfonate molecules contain both hydrophobic and hydrophilic moieties. Lignosulfonates are low-value products with limited performance and are used as such as binders, surfactants, and plasticizers in concrete. Lignosulfonates face strong competition from synthetic petroleum-based plasticizers with superior quality. Therefore, increasing the performance of lignosulfonates is desirable not only from a sustainability point of view but also to expand their usage. One important aspect that describes how well lignosulfonates can act as plasticizers is the molecular weight. In this paper, the molecular weight of four commercial lignosulfonates is increased through oxidation by two laccases without utilization of mediators. Different parameters to obtain maximal molecular weight increase were identified and the technical significance of the experiments is discussed.
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Lacase/metabolismo , Lignina/análogos & derivados , Catálise , Cromatografia em Gel , Lignina/química , Lignina/metabolismo , Peso Molecular , Oxirredução , Espectroscopia de Infravermelho com Transformada de FourierRESUMO
In order to investigate the importance of the monomeric gamma-carbon chemistry in lignin biopolymerization and structure, synthetic lignins (dehydrogenation polymers; DHP) were made from monomers with different degrees of oxidation at the gamma-carbon, i.e., carboxylic acid, aldehyde and alcohol. All monomers formed a polymeric material through enzymatic oxidation. The polymers displayed similar sizes by size exclusion chromatography analyses, but also exhibited some physical and chemical differences. The DHP made of coniferaldehyde had poorer solubility properties than the other DHPs, and through contact angle of water measurement on spin-coated surfaces of the polymeric materials, the DHPs made of coniferaldehyde and carboxylic ferulic acid exhibited higher hydrophobicity than the coniferyl alcohol DHP. A structural characterization with (13)C NMR revealed major differences between the coniferyl alcohol-based polymer and the coniferaldehyde/ferulic acid polymers, such as the predominance of aliphatic double bonds and the lack of certain benzylic structures in the latter cases. The biological role of the reduction at the gamma-carbon during monolignol biosynthesis with regard to lignin polymerization is discussed.