Polymer shape-memory aerogels (PSMAs) are prospects in various fields of application ranging from aerospace to biomedicine, as advanced thermal insulators, actuators, or sensors. However, the fabrication of PSMAs with good mechanical performance is challenging and is currently dominated by fossil-based polymers. In this work, strong, shape-memory bio-aerogels with high specific surface areas (up to 220 m²/g) and low radial thermal conductivity (0.042 W/mK) were prepared through a one-step treatment of native wood using an ionic liquid mixture of [MTBD]⁺[MMP]^-/DMSO. The aerogel showed similar chemical composition similar to native wood. Nanoscale spatial rearrangement of wood biopolymers in the cell wall and lumen was achieved, resulting in flexible hydrogels, offering design freedom for subsequent aerogels with intricate geometries. Shape-memory function under stimuli of water was reported. The chemical composition and distribution, morphology, and mechanical performance of the aerogel were carefully studied using confocal Raman spectroscopy, AFM, SAXS/WAXS, NMR, digital image correlation, etc. With its simplicity, sustainability, and the broad range of applicability, the methodology developed for nanoscale reassembly of wood is an advancement for the design of biobased shape-memory aerogels.

Eco-friendly materials with superior thermal insulation and mechanical properties are desirable for improved energy- and space-efficiency in buildings. Cellulose aerogels with structural anisotropy could fulfill these requirements, but complex processing and high energy demand are challenges for scaling up. Here we propose a scalable, nonadditive, top-down fabrication of strong anisotropic aerogels directly from wood with excellent, near isotropic thermal insulation functions. The aerogel was obtained through cell wall dissolution and controlled precipitation in lumen, using an ionic liquid (IL) mixture comprising DMSO and a guanidinium phosphorus-based IL [MTBD][MMP]. The wood aerogel shows a unique structure with lumen filled with nanofibrils network. In situ formation of a cellulosic nanofibril network in the lumen results in specific surface areas up to 280 m²/g and high yield strengths >1.2 MPa. The highly mesoporous structure (average pore diameter ∼20 nm) of freeze-dried wood aerogels leads to low thermal conductivities in both the radial (0.037 W/mK) and axial (0.057 W/mK) directions, showing great potential as scalable thermal insulators. This synthesis route is energy efficient with high nanostructural controllability. The unique nanostructure and rare combination of strength and thermal properties set the material apart from comparable bottom-up aerogels. This nonadditive synthesis approach is believed to contribute significantly toward large-scale design and structure control of biobased aerogels.

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 ([P₄₄₄₄][OAc]):DMSO-d₆, 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 T₂correction 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.Graphic