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The use of organic solvents in academic research and industry applications is facing increasing regulatory pressure due to environmental and health concerns. Consequently, there is a growing demand for sustainable solvents, particularly in the enzymatic synthesis and processing of polyesters. Biocatalysts offer a sustainable method for producing these materials; however, achieving high molecular weights often necessitates use of solvents. In this work, we introduce a new class of alternative aprotic solvents with medium polarity produced directly from agricultural waste biomass in up to 83 mol % yield (on xylan basis). The new solvents have a largely unmodified xylose core and acetal functionality, yet they show no peroxide formation and provide reduced flammability risk. We also demonstrate their successful application in enzymatic polycondensation reactions with Candida antarctica lipase B (CaLB). In particular, the solvent dibutylxylose (DBX) outperformed the hazardous solvent diphenyl ether and facilitated polycondensation of the lignin-derived diester pyridine-2,4-dicarboxylate, yielding polyesters with a M n of >15 kDa. Computational modelling studies provided further insight into the molecular structure and dynamics of CaLB in the presence of new solvents. Lastly, up to 98 wt % of the new xylose acetals were successfully recovered and recycled, further contributing to the sustainability of the overall process., (© 2024 The Author(s). ChemSusChem published by Wiley-VCH GmbH.)

Nuclear magnetic resonance (NMR) is an important method for structure elucidation of proteins, as it is an easily accessible and well understood method. To characterize intrinsically disordered proteins (IDPs) using computational models it is often necessary to analyze and integrate calculated observables with measurements derived from solution NMR experiments. In this case study, we investigate whether and which chemical shifts of the proline-rich region of Tau protein (residues 210-240) offer information about the conformational state to distinguish two different microscopic conformers. Using multiple computational methods, the chemical shifts of these two conformationally distinct structures are calculated. The different methods are compared regarding their ability to compute chemical shifts that are sensitive to conformational change. The analysis of the data shows significant differences between the available methods and gives suggestions for an improved pathway for ensemble reweighting. Nevertheless, the variation in the chemical shifts which are predicted for configurations that are commonly considered to belong to the same conformation is such that this obscures a comparison between distinct conformations. Conformational sensitivity is found for up to ∼26% of calculated chemical shifts. It is found to be unrelated to the atom element and has a minor relationship with the change in the corresponding ϕ dihedral angle.