| 1. |
- Balakshin, Mikhail, et al.
(författare)
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New opportunities in the valorization of technical lignins
- 2017
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Ingår i: 19th International symposium on wood, fibre and pulping chemistry, August 28 - September 1, 2017, Porto Seguro, Brazil. ; , s. 178-182
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Konferensbidrag (refereegranskat)abstract
- Commercialization of lignins for high-value products should dramatically improve the biorefinery economy and help the growing industry to overcome current economical challenges. However, this requires lignin engineering to obtain products with optimized characteristics for specific applications. This paper reviews important issues of lignin engineering, such as developments in lignin structural analysis, application of small-scale high throughput methods to evaluate lignin performance as well as new achievements in valorization of biorefinery lignins (lignin-cellulose synergism, green and cost efficient methods to upgrade crude biorefinery lignins). These recent developments allow a reconsideration of biorefinery lignins as highvalue products for different applications.
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| 2. |
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| 3. |
- Balakshin, Mikhail, et al.
(författare)
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Spruce milled wood lignin : Linear, branched or cross-linked?
- 2020
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Ingår i: Green Chemistry. - : Royal Society of Chemistry. - 1463-9262 .- 1463-9270. ; 22:13, s. 3985-4001
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Tidskriftsartikel (refereegranskat)abstract
- The subject of lignin structure, critical for fundamental and practical reasons, is addressed in this study that includes a review of the methods applied to elucidate macromolecular branching. The recently available approaches for determination of the absolute molecular mass of spruce milled wood lignin (MWL) along with the quantification of terminal groups clearly indicate that MWL is significantly branched and cross-linked (with ∼36% lignin units partaking in these linkages). Results from independent methods imply that about half of the branching and crosslinking linkages involve aromatic rings, predominantly 5-5′ etherified units; meanwhile, a significant number of linkages are located in the side chains. Quantitative 13C NMR analyses suggest that the branches involve different aliphatic ether (alkyl-O-alkyl) types at the α- and γ-positions of the side chain, with intact β-O-4 linkages. While the exact structures of these moieties require further investigation, our results point to the fact that conventional lignification theory disagrees with the presence of such key moieties in softwood MWL and the observed high degree of branching/crosslinking. Potential reasons for the noted discrepancies are discussed.
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| 4. |
- Balakshin, Mikhail Yu, et al.
(författare)
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New Opportunities in the Valorization of Technical Lignins.
- 2021
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Ingår i: ChemSusChem. - : Wiley. - 1864-5631 .- 1864-564X. ; 14:4, s. 1016-1036
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Tidskriftsartikel (refereegranskat)abstract
- Sugar-based biorefineries have faced significant economic challenges. Biorefinery lignins are often classified as low-value products (fuel or low-cost chemical feedstock) mainly due to low lignin purities in the crude material. However, recent research has shown that biorefinery lignins have a great chance of being successfully used as high-value products, which in turn should result in an economy renaissance of the whole biorefinery idea. This critical review summarizes recent developments from our groups, along with the state-of-the-art in the valorization of technical lignins, with the focus on biorefinery lignins. A beneficial synergistic effect of lignin and cellulose mixtures used in different applications (wood adhesives, carbon fiber and nanofibers, thermoplastics) has been demonstrated. This phenomenon causes crude biorefinery lignins, which contain a significant amount of residual crystalline cellulose, to perform superior to high-purity lignins in certain applications. Where previously specific applications required high-purity and/or functionalized lignins with narrow molecular weight distributions, simple green processes for upgrading crude biorefinery lignin are suggested here as an alternative. These approaches can be easily combined with lignin micro-/nanoparticles (LMNP) production. The processes should also be cost-efficient compared to traditional lignin modifications. Biorefinery processes allow much greater flexibility in optimizing the lignin characteristics desirable for specific applications than traditional pulping processes. Such lignin engineering, at the same time, requires an efficient strategy capable of handling large datasets to find correlations between process variables, lignin structures and properties and finally their performance in different applications.
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| 5. |
- Capanema, Ewellyn, et al.
(författare)
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Application of Omno polymers in PF wood adhesives
- 2017
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Ingår i: 19th International symposium on wood, fibre and pulping chemistry, August 28 - September 1, 2017, Porto Seguro, Brazil. ; , s. 65-69
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Konferensbidrag (refereegranskat)abstract
- The Plantrose® technology is a promising biorefinery method which enables the production of C5 and C6 sugars from different lignocellulosics using sub- and supercritical water in a two-step process. The lignin rich solids after carbohydrate hydrolysis containing various amounts of residual cellulose are trademarked as OmnoTM polymers. The reactivity and bonding performance of different Omno polymers in direct partial substitution of phenol-formaldehyde adhesive resins (PF) for the manufacture of oriented strand board (OSB) and softwood plywood were evaluated by a fast bench screening test using the Automatic Bond Evaluation System (ABES) and by pilot trials on the production and testing of wood panels. The results showed that about 1/3 of commercial glues could be successfully substituted by Omno polymers without any significant drop in the adhesive reactivity and properties of the resulting wood panels. Selected Omno polymers had superior performance as compared to high-purity pulping lignins (Kraft, soda and organosolv) due to a positive effect of the residual cellulose in the Omnopolymers on the adhesive performance. Hardwood lignins had no disadvantages as compared to various softwood lignins, in strict contrast to the current dogma.
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| 6. |
- Diment, Daryna, et al.
(författare)
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A New Methodology to Elucidate Lignin Structure-Properties-Performance Correlation
- 2022
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Konferensbidrag (refereegranskat)abstract
- Unveiling the interrelation between the lignin structure, its properties and performance inspecific applications is of primary importance for lignin engineering for high-value products.Herein, we suggest a new efficient methodology to quantitatively evaluate the roles of ligninspecific functionalities in selected applications. The method is based on changing only onestructural variable at a time, while keeping all others constant prior to performance evaluation.Indulin AT (a softwood Kraft lignin) was subjected to a set of chemical modifications byselectively masking its aliphatic (AlipOH), phenolic OH (PhOH), carboxyl (COOH) andcarbonyl (CO) groups. The property-performance correlation was demonstrated by measuringthe glass transition temperatures (Tg) of the modified lignins. The effect of the modificationson the adsorption performance of the modified lignins was evaluated towards methylene blue.This approach clearly demonstrated that PhOH and AlipOH groups have about equalcontribution (50% each) to the lignin adsorption capacity, while the role of the other functionalgroups is insignificant.
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| 7. |
- Diment, Daryna, et al.
(författare)
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Study toward a More Reliable Approach to Elucidate the Lignin Structure–Property–Performance Correlation
- 2024
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Ingår i: Biomacromolecules. - : American Chemical Society (ACS). - 1525-7797 .- 1526-4602. ; 25:1, s. 200-212
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Tidskriftsartikel (refereegranskat)abstract
- The correlation between lignin structure, its properties, and performance is crucial for lignin engineering in high-value products. Currently, a widespread approach is to compare lignins which differ by more than one parameter (i.e., Kraft vs organosolv vs lignosulfonates) in various applications by attributing the changes in their properties/performance specifically to a certain variable (i.e., phenolic −OH groups). Herein, we suggest a novel approach to overcome this issue by changing only one variable at a time while keeping all others constant before investigating the lignin properties/performance. Indulin AT (Ind-AT), a softwood Kraft lignin, was chosen as the model substrate for this study. Selective (analytical) lignin modifications were used to mask/convert specific functionalities, such as aliphatic (AliphOH) including benzylic −OH (BenzOH) and phenolic −OH (PhOH) groups, carboxyl groups (−COOH) and carbonyl groups (CO) via methylation, acetylation, and reduction. The selectivity and completeness of the reactions were verified by comprehensive NMR analysis (31P and 2D HSQC) of the modified preparations together with state-of-the-art molar mass (MM) characterization. Methylene blue (MB) adsorption, antioxidant activity, and glass transition temperature (Tg) were used to demonstrate and compare the properties/performance of the obtained modified lignins. We found that the contribution of different functionalities in the adsorption of MB follows the trend BenzOH > −COOH > AlipOH > PhOH. Noteworthy, benzylic −OH contributes ca. 3 and 2.3 times more than phenolic and aliphatic −OH, respectively. An 11% and 17% increase of Tg was observed with respect to the unmodified Indulin by methylating benzylic −OH groups and through reduction, respectively, while full acetylation/methylation of aliphatic and phenolic −OH groups resulted in lower Tg. nRSI experiments revealed that phenolic −OH play a crucial role in increasing the antioxidant activity of lignin, while both aliphatic −OH groups and −COOHs possess a detrimental effect, most likely due to H-bonding. Overall, for the first time, we provide here a reliable approach for the engineering of lignin-based products in high value applications by disclosing the role of specific lignin functionalities.
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| 8. |
- Giummarella, Nicola, et al.
(författare)
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Nativity of lignin carbohydrate bonds substantiated by biomimetic synthesis
- 2019
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Ingår i: Journal of Experimental Botany. - : Oxford University Press. - 0022-0957 .- 1460-2431. ; 70:20, s. 5591-5601
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Tidskriftsartikel (refereegranskat)abstract
- The question of whether lignin is covalently linked to carbohydrates in native wood, forming what is referred to as lignin–carbohydrate complexes (LCCs), still lacks unequivocal proof. This is mainly due to the need to isolate lignin from woody materials prior to analysis, under conditions leading to partial chemical modification of the native wood polymers. Thus, the correlation between the structure of the isolated LCCs and LCCs in situ remains open. As a way to circumvent the problematic isolation, biomimicking lignin polymerization in vivo and in vitro is an interesting option. Herein, we report the detection of lignin–carbohydrate bonds in the extracellular lignin formed by tissue-cultured Norway spruce cells, and in modified biomimetic lignin synthesis (dehydrogenation polymers). Semi-quantitative 2D heteronuclear singular quantum coherence (HSQC)-, 31P -, and 13C-NMR spectroscopy were applied as analytical tools. Combining results from these systems, four types of lignin–carbohydrate bonds were detected; benzyl ether, benzyl ester, γ-ester, and phenyl glycoside linkages, providing direct evidence of lignin–carbohydrate bond formation in biomimicked lignin polymerization. Based on our findings, we propose a sequence for lignin–carbohydrate bond formation in plant cell walls.
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| 9. |
- Lizundia, Erlantz, et al.
(författare)
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Multifunctional lignin-based nanocomposites and nanohybrids
- 2021
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Ingår i: Green Chemistry. - : Royal Society of Chemistry (RSC). - 1463-9262 .- 1463-9270. ; 23:18, s. 6698-6760
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Forskningsöversikt (refereegranskat)abstract
- Significant progress in lignins valorization and development of high-performance sustainable materials have been achieved in recent years. Reports related to lignin utilization indicate excellent prospects considering green chemistry, chemical engineering, energy, materials and polymer science, physical chemistry, biochemistry, among others. To fully realize such potential, one of the most promising routes involves lignin uses in nanocomposites and nanohybrid assemblies, where synergistic interactions are highly beneficial. This review first discusses the interfacial assembly of lignins with polysaccharides, proteins and other biopolymers, for instance, in the synthesis of nanocomposites. To give a wide perspective, we consider the subject of hybridization with metal and metal oxide nanoparticles, as well as uses as precursor of carbon materials and the assembly with other biobased nanoparticles, for instance to form nanohybrids. We provide cues to understand the fundamental aspects related to lignins, their self-assembly and supramolecular organization, all of which are critical in nanocomposites and nanohybrids. We highlight the possibilities of lignin in the fields of flame retardancy, food packaging, plant protection, electroactive materials, energy storage and health sciences. The most recent outcomes are evaluated given the importance of lignin extraction, within established and emerging biorefineries. We consider the benefit of lignin compared to synthetic counterparts. Bridging the gap between fundamental and application-driven research, this account offers critical insights as far as the potential of lignin as one of the frontrunners in the uptake of bioeconomy concepts and its application in value-added products.
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| 10. |
- Tarasov, Dmitry, et al.
(författare)
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AqSO biorefinery : a green and parameter-controlled process for the production of lignin-carbohydrate hybrid materials
- 2022
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Ingår i: Green Chemistry. - : Royal Society of Chemistry (RSC). - 1463-9262 .- 1463-9270. ; 24:17, s. 6639-6656
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Tidskriftsartikel (refereegranskat)abstract
- The current biorefineries are focused on the comprehensive fractionation of biomass components into separate lignin and carbohydrate fractions for the production of materials, platform chemicals and biofuel. However, it has become obvious that the combination of lignin and carbohydrates can have significant technical, environmental, and economic benefits as opposed to their separate use. Herein, we developed a green, simple, and flexible biorefinery concept for the integrated utilization of all major biomass components for high-value applications with the focus on functional lignin–carbohydrate hybrids (LCHs). The established process consisted of a modified hydrothermal treatment (HTT) of birch wood followed by solvent extraction of the resulting solids and is therefore named AquaSolv Omni (AqSO) biorefinery. The AqSO biorefinery produces three major streams: hydrolysate (hemicellulose-derived products), solvent-extracted lignin–carbohydrate complexes (LCCs) and cellulose-rich fibers. Specific process conditions were found to facilitate the production of LCCs of different types in high yields as a new valuable and industrially realistic process stream. The effect of the process severity and liquid to solid (L/S) ratio on the yields and compositions of the produced fractions as well as on the structure and properties of the extracted LCCs was investigated using state of the art NMR spectroscopy and molar mass distribution analysis among other methods. The high flexibility of the process allows for engineering of the resulting products in a wide range of chemical compositions, structures and physicochemical properties and therefore gives a good opportunity to optimize the products for specific high-value applications. The process can be easily combined with other biorefinery operations (e.g., enzymatic hydrolysis, pulping, bleaching) to be incorporated into existing value chains or create new ones and thus is suitable for different biorefinery scenarios. First examples of high-value applications of AqSO biorefinery LCHs are reported. LCC nanoparticles (LCCNPs) were produced for the first time directly from the solvent extract and their properties were investigated. LCCNPs could efficiently stabilize Pickering emulsions of tetrahydrofurfuryl methacrylate and allowed their free radical polymerization. In addition, AqSO LCHs showed promising results as wood adhesives. Overall, our results provide detailed information on the complex lignocellulosic fractions and bridge the gap from process engineering to sustainable product development.
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