Recent developments in the area of plant‐based hydrogels are introduced, especially those derived from wood as a widely available, multiscale, and hierarchical source of nanomaterials, as well as other cell wall elements. With water being fundamental in a hydrogel, water interactions, hydration, and swelling, all critically important in designing, processing, and achieving the desired properties of sustainable and functional hydrogels, are highlighted. A plant, by itself, is a form of a hydrogel, at least at given states of development, and for this reason phenomena such as fluid transport, diffusion, capillarity, and ionic effects are examined. These aspects are highly relevant not only to plants, especially lignified tissues, but also to the porous structures produced after removal of water (foams, sponges, cryogels, xerogels, and aerogels). Thus, a useful source of critical and comprehensive information is provided regarding the synthesis of hydrogels from plant materials (and especially wood nanostructures), and about the role of water, not only for processing but for developing hydrogel properties and uses.

Multiphase (emulsion) gels with internal phase fractions between 0.1 and 0.5 were formulated at low loadings of cellulose nanofibrils (CNF), alginate and polylactide (PLA). Their properties (rheology and morphology) fitted those of inks used for direct ink writing (DIW). The effect of formulation and composition variables were elucidated after printing cubic scaffolds and other solid designs. The distinctive microstructures that were developed allowed high printing fidelity and displayed limited shrinkage after room temperature and freeze drying (0 and 5% shrinkage in the out-of-plane and in-plane directions upon freeze drying, respectively). The CNF added in the continuous phase was shown to be critical to achieve rheology control, as an effective interfacial stabilizer and to ensure the printability of the ink toward high structural reliability.We found that the extent of shape retention of the dried scaffolds resulted from the tightly locked internal structure. The PLA that was initially added in the non-polar or organic phase (0 to 2 12%), was randomly embedded in the entire scaffold, providing a strong resistance to shrinkage during the slow water evaporation at ambient temperature. No surface collapse or lateral deformation of the dried scaffolds occurred, indicating that the incorporation of PLA limited drying-induced shape failure. It also reduced compression strain by providing better CNF skeletal support, improving the mechanical strength.Upon re-wetting, the combination of the hydrophilicity imparted by CNF and alginate together with the highly porous structure of the 3D material and the internal micro-channels contributed to high water absorption via capillary and other phenomena (swelling % between ~400 and 900 %). However, no shape changes occurred compared to the initial 3D-printed shape. The swelling of the scaffolds correlated inversely with the PLA content in the precursor emulsion gel, providing a means to regulate the interaction with water given its low surface energy.Overall, the results demonstrate that by compatibilization of the CNF-based hydrophilic and the PLA-based hydrophobic components, it is possible to achieve shape control and retention upon 3D printing, opening the possibility of adopting low-solids inks for DIW into dry objects. The dryable CNF-based 3D structural materials absorb water while being able to support load (high elastic modulus) and maintain the shape upon hydration.

The rapid co‐assembly of graphene oxide (GO) nanosheets and a surfactant at the oil/water (O/W) interface is harnessed to develop a new class of soft materials comprising continuous, multilayer, interpenetrated, and tubular structures. The process uses a microfluidic approach that enables interfacial complexation of two‐phase systems, herein, termed as “liquid streaming” (LS). LS is demonstrated as a general method to design multifunctional soft materials of specific hierarchical order and morphology, conveniently controlled by the nature of the oil phase and extrusion's injection pressure, print‐head speed, and nozzle diameter. The as‐obtained LS systems can be readily converted into ultra‐flyweight aerogels displaying worm‐like morphologies with multiscale porosities (micro‐ and macro‐scaled). The presence of reduced GO nanosheets in such large surface area systems renders materials with outstanding mechanical compressibility and tailorable electrical activity. This platform for engineering soft materials and solid constructs opens up new horizons toward advanced functionality and tunability, as demonstrated here for ultralight printed conductive circuits and electromagnetic interference shields.

Nanocellulose has been demonstrated as a suitable material for cell culturing, given its similarity to extracellular matrices. Taking advantage of the shear thinning behavior, nanocellulose suits three-dimensional (3D) printing into scaffolds that support cell attachment and proliferation. Here, we propose aqueous suspensions of acetylated nanocellulose of a low degree of substitution for direct ink writing (DIW). This benefits from the heterogeneous acetylation of precursor cellulosic fibers, which eases their deconstruction and confers the characteristics required for extrusion in DIW. Accordingly, the morphology of related 3D-printed architectures and their performance during drying and rewetting as well as interactions with living cells are compared with those produced from typical unmodified and TEMPO-oxidized nanocelluloses. We find that a significantly lower concentration of acetylated nanofibrils is needed to obtain bioinks of similar performance, affording more porous structures. Together with their high surface charge and axial aspect, acetylated nanocellulose produces dimensionally stable monolithic scaffolds that support drying and rewetting, required for packaging and sterilization. Considering their potential uses in cardiac devices, we discuss the interactions of the scaffolds with cardiac myoblast cells. Attachment, proliferation, and viability for 21 days are demonstrated. Overall, the performance of acetylated nanocellulose bioinks opens the possibility for reliable and scale-up fabrication of scaffolds appropriate for studies on cellular processes and for tissue engineering.