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Humins, (side-)products of the acid-catalysed dehydration of carbohydrates, will be produced in substantial quantities with the development of industrial biorefining processes. Most structural knowledge about such humins is based on synthetic model humins prepared at lab-scale from typical carbohydrate(-derived) compounds. Here, we report the first extensive characterisation study of an industrial humin. The soluble humin was generated from pilot plant-scale methanolic cyclodehydration of D-fructose to 5-methoxymethyl-2-furfural (MMF), as part of the Avantium YXY® process to produce FDCA. Purification of the industrial humin followed by fractionation allowed isolation of a water-insoluble, high molecular weight fraction (WIPIH) and a water-soluble, low-to-middle molecular weight soluble fraction (WES). Characterisation by elemental analysis, thermogravimetry, IR and NMR spectroscopy and size exclusion chromatography provided a detailed picture of the humin structure in both fractions. Aided by a comprehensive NMR spectral library of furanic model compounds, we identified the main furanic building blocks and inter-unit linkages and propose a structure for this industrial humin sample. The WIPIH and WES fractions were found to be composed of furanic rings interconnected by short aliphatic chains containing a wide range of functionalities including alcohols, ethers, carboxylic acids, esters, aldehydes and ketones. The low level of crosslinking and high functional group content of the industrial humin differ from the more extensively studied, (highly over-)condensed synthetic model humins, towards which they can be considered intermediates. The structural and compositional insights into the nature of an actual industrial humin open up a broad spectrum of valorisation opportunities. [ABSTRACT FROM AUTHOR]

Visualizing a protein's molecular motions has been a long standing topic of research in the biophysics community. Largely this has been done by exploiting nuclear magnetic resonance spectroscopy (NMR), and arguably no protein's molecular motions have been better characterized by NMR than that of ubiquitin (Ub), a 76 amino acid polypeptide essential in ubiquitination-a key regulatory system within cells. Herein, we discuss ubiquitin's conformational plasticity as visualized, at atomic resolution, by more than 35 years of NMR work. In our discussions we point out the differences between data acquired in vitro, ex vivo, as well as in vivo and stress the need to investigate Ub's conformational plasticity in more biologically representative backgrounds., (© 2024 The Author(s). ChemBioChem published by Wiley-VCH GmbH.)

Cross-linking, also called tanning, improves mechanical properties of leather and also increases its enzymatic and thermal stability. As a final product, leather has an ultimate tensile strength (σ) of 8-25 MPa and an elongation at break (ε) of >30 %. Mycelium-based materials are a sustainable alternative to leather. Here, the effect of cross-linkers was assessed on mechanical properties of Schizophyllum commune mycelium sheets . To this end, glutaraldehyde and N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide (EDC) were used as well as extracts of Ligustrum vulgare leaves , and bark of Acacia mearnsii and Caesalpinia spinosa. Untanned sheets had a σ of 7.8 MPa and an ε of 15.2 %, while the best overall combination of strength and elasticity was obtained with 0.1 % glutaraldehyde with a σ of 11.1 MPa and an ε of 14.6 %. Cross-linking also increased enzymatic stability and reduced mycelial water absorption but did not result in increased thermal stability. Fourier transform infrared spectroscopy (FTIR), 1D nuclear magnetic resonance spectroscopy (NMR), and amino acid analysis showed that glutaraldehyde bound both protein amino groups and polysaccharide hydroxyl groups by forming Schiff bases and acetals, respectively. Together, synthetic and vegetable cross-linkers can be used to obtain mycelium materials with leather-like tensile strength., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2024 The Authors.)

Sensitivity enhanced dynamic nuclear polarization solid-state NMR is emerging as a powerful technique for probing the structural properties of conformationally homogenous and heterogenous biomolecular species irrespective of size at atomic resolution within their native environments. Herein we detail advancements that have made acquiring such data, specifically within the confines of intact bacterial and eukaryotic cell a reality and further discuss the type of structural information that can presently be garnered by the technique's exploitation. Subsequently, we discuss bottlenecks that have thus far curbed cellular DNP-ssNMR's broader adoption namely due a lack of sensitivity and spectral resolution. We also explore possible solutions ranging from utilization of new pulse sequences, design of better performing polarizing agents, and application of additional biochemical/ cell biological methodologies., (© 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)