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- Balakshin, Mikhail, et al.
(author)
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Spruce milled wood lignin : Linear, branched or cross-linked?
- 2020
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In: Green Chemistry. - : Royal Society of Chemistry. - 1463-9262 .- 1463-9270. ; 22:13, s. 3985-4001
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Journal article (peer-reviewed)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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- Balakshin, Mikhail Yu, et al.
(author)
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New Opportunities in the Valorization of Technical Lignins.
- 2021
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In: ChemSusChem. - : Wiley. - 1864-5631 .- 1864-564X. ; 14:4, s. 1016-1036
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Journal article (peer-reviewed)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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- Bergmann, Matthias, et al.
(author)
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Transdisciplinary sustainability research in real-world labs: success factors and methods for change
- 2021
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In: Sustainability Science. - : Springer Science and Business Media LLC. - 1862-4057 .- 1862-4065. ; 16:2, s. 541-564
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Journal article (peer-reviewed)abstract
- The transdisciplinary research mode has gained prominence in the research on and for sustainability transformations. Yet, solution-oriented research addressing complex sustainability problems has become complex itself, with new transdisciplinary research formats being developed and tested for this purpose. Application of new formats offers learning potentials from experience. To this end, we accompanied fourteen research projects conceptualized as real-world labs (RwLs) from 2015 to 2018. RwLs were part of a funding program on ‘Science for Sustainability’ in the German federal state of Baden-Württemberg. Here, we combine conceptual and empirical work to a structured collection of experiences and provide a comprehensive account of RwLs. First, we outline characteristics of RwLs as transformation oriented, transdisciplinary research approach, using experiments, enabling learning and having a long-term orientation. Second, we outline eleven success factors and concrete design notes we gained through a survey of the 14 RwLs: (1) find the right balance between scientific and societal aims, (2) address the practitioners needs and restrictions, (3) make use of the experimentation concept, (4) actively communicate, (5) develop a ‘collaboration culture’, (6) be attached to concrete sites, (7) create lasting impact and transferability, (8) plan for sufficient time and financial means, (9) adaptability, (10) research-based learning, and (11) recognize dependency on external actors. Characteristics and success factors are combined to illustrate practical challenges in RwLs. Third, we show which methods could be used to cope with challenges in RwLs. We conclude discussing the state of debate on RwLs and outline future avenues of research.
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- Koso, Tetyana, et al.
(author)
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2D Assignment and quantitative analysis of cellulose and oxidized celluloses using solution-state NMR spectroscopy
- 2020
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In: Cellulose. - : Springer Science and Business Media LLC. - 0969-0239 .- 1572-882X. ; 27:14, s. 7929-7953
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Journal article (peer-reviewed)abstract
- The limited access to fast and facile general analytical methods for cellulosic and/or biocomposite materials currently stands as one of the main barriers for the progress of these disciplines. To that end, a diverse set of narrow analytical techniques are typically employed that often are time-consuming, costly, and/or not necessarily available on a daily basis for practitioners. Herein, we rigorously demonstrate a general quantitative NMR spectroscopic method for structural determination of crystalline cellulose samples. Our method relies on the use of a readily accessible ionic liquid electrolyte, tetrabutylphosphonium acetate ([P-4444][OAc]):DMSO-d(6), for the direct dissolution of biopolymeric samples. We utilize a series of model compounds and apply now classical (nitroxyl-radical and periodate) oxidation reactions to cellulose samples, to allow for accurate resonance assignment, using 2D NMR. Quantitative heteronuclear single quantum correlation (HSQC) was applied in the analysis of key samples to assess its applicability as a high-resolution technique for following cellulose surface modification. Quantitation using HSQC was possible, but only after applying T(2)correction to integral values. The comprehensive signal assignment of the diverse set of cellulosic species in this study constitutes a blueprint for the direct quantitative structural elucidation of crystalline lignocellulosic, in general, readily available solution-state NMR spectroscopy. [GRAPHICS] .
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