Nanoarchitectonics of Nanocellulose Filament Electrodes by Femtosecond Pulse Laser Deposition of ZnO and In Situ Conjugation of Conductive Polymers.

Electroactive filament electrodes were synthesized by wet-spinning of cellulose nanofibrils (CNF) followed by femtosecond pulse laser deposition of ZnO (CNF@ZnO). A layer of conducting conjugated polymers was further adsorbed by in situ polymerization of either pyrrole or aniline, yielding systems optimized for electron conduction. The resultant hybrid filaments were thoroughly characterized by imaging, spectroscopy, electrochemical impedance, and small- and wide-angle X-ray scattering. For the filaments using polyaniline, the measured conductivity was a result of the synergy between the inorganic and organic layers, while the contribution was additive in the case of the systems containing polypyrrole. This observation is rationalized by the occurrence of charge transfer between ZnO and polyaniline but not that with polypyrrole. The introduced conductive hybrid filaments displayed a performance that competes with that of metallic counterparts, offering great promise for next-generation filament electrodes based on renewable nanocellulose.

Monodispersed Renewable Particles by Cascade and Density Gradient Size Fractionation to Advance Lignin Nanotechnologies.

Control over particle size and shape heterogeneity is highly relevant to the design of photonic coatings and supracolloidal assemblies. Most developments in the area have relied on mineral and petroleum-derived polymers that achieve well-defined chemical and dimensional characteristics. Unfortunately, it is challenging to attain such control when considering renewable nanoparticles. Herein, a pathway toward selectable biobased particle size and physicochemical profiles is proposed. Specifically, lignin is fractionated, a widely available heterogeneous polymer that can be dissolved in aqueous solution, to obtain a variety of monodispersed particle fractions. A two-stage cascade and density gradient centrifugation that relieves the need for solvent pre-extraction or other pretreatments but achieves particle bins of uniform size (~60 to 860 nm and polydispersity, PDI<0.06, dynamic light scattering) along with characteristic surface chemical features is introduced. It is found that the properties and associated colloidal behavior of the particles are suitably classified in distinctive size populations, namely, i) nanoscale (50-100 nm), ii) photonic (100-300 nm) and iii) near-micron (300-1000 nm). The strong correlation that exists between size and physicochemical characteristics (molar mass, surface charge, bonding and functional groups, among others) is introduced as a powerful pathway to identify nanotechnological uses that benefit from the functionality and cost-effectiveness of biogenic particles.

Surface charge manipulation for improved humidity sensing of TEMPO-oxidized cellulose nanofibrils.

Cellulose-based humidity sensors have attracted great research interest due to their hydrophilicity, biodegradability, and low cost. However, they still suffer from relatively low humidity sensitivity. Due to the presence of negatively charged carboxylate groups, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized cellulose nanofibril (CNF) exhibits enhanced hydrophilicity and ion conductivity, which is considered a promising candidate for humidity sensing. In this work, we developed a facile strategy to improve the humidity sensitivity of CNF films by regulating their surface charge density. With the increase in surface charge density, both water uptake and charge carrier densities of the CNF films can be improved, enabling a humidity sensitivity of up to 44.5 % (%RH)-1, higher than that of most polymer-based humidity sensors reported in the literature. Meanwhile, the sensor also showed good linearity (R2 = 0.998) over the 15-75 % RH at 1 kHz. With these features, the CNF film was further demonstrated for applications in noncontact sensing, such as human respiration, moisture on fingertips, and water leakage, indicating the great potential of CNF film in humidity monitoring.

Processing factors affecting roughness, optical and mechanical properties of nanocellulose films for optoelectronics.

This work aims to understand how nanocellulose (NC) processing can modify the key characteristics of NC films to align with the main requirements for high-performance optoelectronics. The performance of these devices relies heavily on the light transmittance of the substrate, which serves as a mechanical support and optimizes light interactions with the photoactive component. Critical variables that determine the optical and mechanical properties of the films include the morphology of cellulose nanofibrils (CNF), as well as the concentration and turbidity of the respective aqueous suspensions. This study demonstrates that achieving high transparency was possible by reducing the grammage and adjusting the drying temperature through hot pressing. Furthermore, the use of modified CNF, specifically carboxylated CNF, resulted in more transparent films due to a higher nanosized fraction and lower turbidity. The mechanical properties of the films depended on their structure, homogeneity (spatial uniformity of local grammage), and electrokinetic factors, such as the presence of electrostatic charges on CNF. Additionally, we investigated the angle-dependent transmittance of the CNF films, since solar devices usually operate under indirect light. This work demonstrates the importance of a systematic approach to the optimization of cellulose films, providing valuable insight into the optoelectronic field.

Benchmarking the Humidity-Dependent Mechanical Response of (Nano)fibrillated Cellulose and Dissolved Polysaccharides as Sustainable Sand Amendments.

Soil quality is one of the main limiting factor in the development of the food sector in arid areas, mainly due to its poor mechanics and lack of water retention. Soil's organic carbon is nearly absent in arid soils, though it is important for water and nutrient transport, to soil mechanics, to prevent erosion, and as a long-term carbon sink. In this study, we evaluate the potential benefits that are brought to inert sand by the incorporation of a range of, mainly, cellulosic networks in their polymeric or structured (fiber) forms, analogously to those found in healthy soils. We explore the impact of a wide range of nonfood polysaccharide-based amendments, including pulp fibers, nanocellulose, cellulose derivatives, and other readily available polysaccharide structures derived from arthropods (chitosan) or fruit peels (pectin) residues. A practical methodology is presented to form sand-polymer composites, which are evaluated for their soil mechanics as a function of humidity and the dynamics of their response to water. The mechanics are correlated to the network of polymers formed within the pores of the sandy soil, as observed by electron microscopy. The response to water is correlated to both the features of the network and the individual polysaccharides' physicochemical features. We expect this work to provide a rapid and reproducible methodology to benchmark sustainable organic amendments for arid soils.

Multiphase Under-Liquid Biofabrication With Living Soft Matter: A Route to Customize Functional Architectures With Microbial Nanocellulose.

The growth of aerobic microbes at air-water interfaces typically leads to biofilm formation. Herein, a fermentative alternative that relies on oil-water interfaces to support bacterial activity and aerotaxis is introduced. The process uses under-liquid biofabrication by structuring bacterial nanocellulose (BNC) to achieve tailorable architectures. Cellulose productivity in static conditions is first evaluated using sets of oil homologues, classified in order of polarity. The oils are shown for their ability to sustain bacterial growth and BNC production according to air transfer and solubilization, both of which impact the physiochemical properties of the produced biofilms. The latter are investigated in terms of their morphological (fibril size and network density), structural (crystallinity) and physical-mechanical (surface area and strength) features. The introduced under-liquid biofabrication is demonstrated for the generation of BNC-based macroscale architectures and compartmentalized soft matter. This can be accomplished following three different routes, namely, 3D under-liquid networking (multi-layer hydrogels/composites), emulsion templating (capsules, emulgels, porous materials), and anisotropic layering (Janus membranes). Overall, the proposed platform combines living matter and multi-phase systems as a robust option for material development with relevance in biomedicine, soft robotics, and bioremediation, among others.

Solid Wood Modification toward Anisotropic Elastic and Insulative Foam-Like Materials.

The methods used to date to produce compressible wood foam by top-down approaches generally involve the removal of lignin and hemicelluloses. Herein, we introduce a route to convert solid wood into a super elastic and insulative foam-like material. The process uses sequential oxidation and reduction with partial removal of lignin but high hemicellulose retention (process yield of 72.8%), revealing fibril nanostructures from the wood's cell walls. The elasticity of the material is shown to result from a lamellar structure, which provides reversible shape recovery along the transverse direction at compression strains of up to 60% with no significant axial deformation. The compressibility is readily modulated by the oxidation degree, which changes the crystallinity and mobility of the solid phase around the lumina. The performance of the highly resilient foam-like material is also ascribed to the amorphization of cellulosic fibrils, confirmed by experimental and computational (molecular dynamics) methods that highlight the role of secondary interactions. The foam-like wood is optionally hydrophobized by chemical vapor deposition of short-chained organosilanes, which also provides flame retardancy. Overall, we introduce a foam-like material derived from wood based on multifunctional nanostructures (anisotropically compressible, thermally insulative, hydrophobic, and flame retardant) that are relevant to cushioning, protection, and packaging.

Liquid-templated graphene aerogel electromagnetic traps.

For decades, the inherently reflective nature of metallic electromagnetic (EM) shields and their induced secondary EM pollution have posed significant challenges for sensitive electronics. While numerous efforts have been made to develop superior EM shielding systems, the issue of reflection dominancy in metallic substrates remains unresolved. Herein, we addressed this long-lasting obstacle by pairing metallic shields with ultra-lightweight (density of 3.12-3.40 mg cm-3) elastic anti-reflection aerogels, altering their shielding mechanism from dominant reflection (reflectance >0.8) to absorption (absorbance >0.7) by trapping EM waves inside the aerogel. The aerogel EM traps were generated using interfacial complexation, yielding engineerable filamentous liquid structures. These served as templates for aerogel creation through a follow-up process of freezing and lyophilization. The engineerable lossy medium of aerogels benefits from a multi-scale porous construct with the combined action of dielectric and conduction losses, highly dissipating the EM waves and minimizing the reflections. Notably, declining the diameter of aerogel filaments promoted its absorption dominancy, rendering it a potent dissipating medium for EM waves. Pairing a metallic substrate with filamentous aerogel EM traps has resulted in an exceptionally effective absorption-dominant shielding system, achieving absorbance levels between 0.70-0.81. This system offers a shielding effectiveness of 53-89 dB within the X-band frequency range. This innovation addresses a persistent issue in shielding science related to the reflective characteristics of metallic substrates, effectively inhibiting their induced EM reflections.

Controlling the Nematic Liquid Crystallinity of Cellulose Nanocrystals with an Alcohol Ethoxy Sulfonate Surfactant.

Cellulose nanocrystals (CNCs) are biobased colloidal nanorods that have unlocked new opportunities in the area of sustainable functional nanomaterials including structural films and coatings, biomedical devices, energy, sensing, and composite materials. While selective light reflection and sensing develop from the typical chiral nematic (cholesteric, Nem*) liquid crystallinity exhibited by CNCs, a wealth of technologies would benefit from a nematic liquid crystal (LC) with CNC uniaxial alignment. Therefore, this study answers the central question of whether surfactant complexation suppresses CNC chirality in favor of nematic lyotropic and thermotropic liquid crystallinity. Therein, we use a common surfactant having both nonionic and anionic blocks, namely, oligo(ethylene glycol) alkyl-3-sulfopropyl diether potassium salt (an alcohol ethoxy sulfonate (AES)). AES forms complexes with CNCs in toluene (a representative for nonpolar organic solvent) via hydrogen bonding with an AES' oligo(ethylene glycol) block. A sufficiently high AES weight fraction endows the dispersibility of CNC in toluene. Lyotropic liquid crystallinity with Schlieren textures containing two- and four-point brush defects is observed in polarized optical microscopy (POM), along with the suppression of the cholesteric fingerprint textures. The results suggest a nematic (Nem) phase in toluene. Moreover, thermotropic liquid crystallinity is observed by incorporating an excess of AES, in the absence of an additional solvent and upon mild heating. The Schlieren textures suggest a nematic system that undergoes uniaxial alignment under mild shear. Importantly, replacing AES with a corresponding nonionic surfactant does not lead to liquid crystalline properties, suggesting electrostatic structural control of the charged end group of AES. Overall, we introduce a new avenue to suppress CNC chirality to achieve nematic structures, which resolves the long-sought uniaxial alignment of CNCs in filaments, composite materials, and optical devices.

Biobased and biodegradable films exhibiting circularly polarized room temperature phosphorescence.

There is interest in developing sustainable materials displaying circularly polarized room-temperature phosphorescence, which have been scarcely reported. Here, we introduce biobased thin films exhibiting circularly polarized luminescence with simultaneous room-temperature phosphorescence. For this purpose, phosphorescence-active lignosulfonate biomolecules are co-assembled with cellulose nanocrystals in a chiral construct. The lignosulfonate is shown to capture the chirality generated by cellulose nanocrystals within the films, emitting circularly polarized phosphorescence with a 0.21 dissymmetry factor and 103 ms phosphorescence lifetime. By contrast with most organic phosphorescence materials, this chiral-phosphorescent system possesses phosphorescence stability, with no significant recession under extreme chemical environments. Meanwhile, the luminescent films resist water and humid environments but are fully biodegradable (16 days) in soil conditions. The introduced bio-based, environmentally-friendly circularly polarized phosphorescence system is expected to open many opportunities, as demonstrated here for information processing and anti-counterfeiting.

Innovations in hydrogel-based manufacturing: A comprehensive review of direct ink writing technique for biomedical applications.

Direct ink writing (DIW) stands as a pioneering additive manufacturing technique that holds transformative potential in the field of hydrogel fabrication. This innovative approach allows for the precise deposition of hydrogel inks layer by layer, creating complex three-dimensional structures with tailored shapes, sizes, and functionalities. By harnessing the versatility of hydrogels, DIW opens up possibilities for applications spanning from tissue engineering to soft robotics and wearable devices. This comprehensive review investigates DIW as applied to hydrogels and its multifaceted applications. The paper introduces a diverse range of printing techniques while providing a thorough exploration of DIW for hydrogel-based printing. The investigation aims to explain the progress made, challenges faced, and potential trajectories that lie ahead for DIW in hydrogel-based manufacturing. The fundamental principles underlying DIW are carefully examined, specifically focusing on rheological attributes and printing parameters, prompting a comprehensive survey of the wide variety of hydrogel materials. These encompass both natural and synthetic variations, all of which can be effectively harnessed for this purpose. Furthermore, the review explores the latest applications of DIW for hydrogels in biomedical areas, with a primary focus on tissue engineering, wound dressing, and drug delivery systems. The document not only consolidates the existing state of DIW within the context of hydrogel-based manufacturing but also charts potential avenues for further research and innovative breakthroughs.

Lignin beyond the status quo: recent and emerging composite applications.

The demand for biodegradable materials across various industries has recently surged due to environmental concerns and the need for the adoption of renewable materials. In this context, lignin has emerged as a promising alternative, garnering significant attention as a biogenic resource that endows functional properties. This is primarily ascribed to its remarkable origin and structure that explains lignin's capacity to bind other molecules, reinforce composites, act as an antioxidant, and endow antimicrobial effects. This review summarizes recent advances in lignin-based composites, with particular emphasis on innovative methods for modifying lignin into micro and nanostructures and evaluating their functional contribution. Indeed, lignin-based composites can be tailored to have superior physicomechanical characteristics, biodegradability, and surface properties, thereby making them suitable for applications beyond the typical, for instance, in ecofriendly adhesives and advanced barrier technologies. Herein, we provide a comprehensive overview of the latest progress in the field of lignin utilization in emerging composite materials.

Hollow Filaments from Coaxial Dry-Jet Wet Spinning of a Cellulose Solution in an Ionic Liquid: Wet-Strength and Water Interactions.

Hollow tubing and tubular filaments are highly relevant to membrane technologies, vascular tissue engineering, and others. In this context, we introduce hollow filaments (HF) produced through coaxial dry-jet wet spinning of cellulose dissolved in an ionic liquid ([emim][OAc]). The HF, developed upon regeneration in water (23 °C), displays superior mechanical performance (168 MPa stiffness and 60% stretchability) compared to biobased counterparts, such as those based on collagen. The results are rationalized by the effects of crystallinity, polymer orientation, and other factors associated with rheology, thermal stability, and dynamic vapor sorption. The tensile strength and strain of the HF (dry and wet) are enhanced by drying and wetting cycles (water vapor sorption and desorption experiments). Overall, we unveil the role of water molecules in the wet performance of HF produced by cellulose regeneration from [emim][OAc], which offers a basis for selecting suitable applications.

Structured Emulgels by Interfacial Assembly of Terpenes and Nanochitin.

Interfacial assemblies formed by colloidal complexation are effective in multiphase stabilization, as shown in structured liquids and Pickering emulgels. Herein, we demonstrate a type of biobased colloidal system that spontaneously stabilizes an organic phase in a continuous hydrogel phase. Specifically, a triterpene extracted from bark (betulin, BE) is added to an organic phase containing a coniferous resin (rosin acid, a diterpene). BE is shown to take part in strong noncovalent interactions with the nanochitin dispersed in the aqueous (hydrogel) phase, leading to a complex of high interfacial activity. The viscoelastic response of the system is rationalized by the presence of a superstable structured dual network. When used as a templating material, the emulgel develops into structured liquids and cryogels. The herein introduced all-biobased type of nanoparticle surfactant system forms a gel ("emulsion-filled" with "aggregated droplets") that features the functional benefits of both betulin and nanochitin.

Wood-based superblack.

Light is a powerful and sustainable resource, but it can be detrimental to the performance and longevity of optical devices. Materials with near-zero light reflectance, i.e. superblack materials, are sought to improve the performance of several light-centered technologies. Here we report a simple top-down strategy, guided by computational methods, to develop robust superblack materials following metal-free wood delignification and carbonization (1500 °C). Subwavelength severed cells evolve under shrinkage stresses, yielding vertically aligned carbon microfiber arrays with a thickness of ~100 µm and light reflectance as low as 0.36% and independent of the incidence angle. The formation of such structures is rationalized based on delignification method, lignin content, carbonization temperature and wood density. Moreover, our measurements indicate a laser beam reflectivity lower than commercial light stoppers in current use. Overall, the wood-based superblack material is introduced as a mechanically robust surrogate for microfabricated carbon nanotube arrays.

Hollow N-doped carbon nano-mushroom encapsulated hybrid Ni3S2/Fe5Ni4S8 particle anchored to the inner wall of porous wood carbon for efficient oxygen evolution electrocatalysis.

Structural design and morphology engineering are considered significant strategies to boost the catalytic performance of electrocatalysts toward the oxygen evolution reaction. Inspired by the natural porosity and abundant functional groups, herein, hollow N-doped carbon nano-mushroom (NCNM) encapsulated hybrid sulfide particles rooted into a carbonized wood (CW) framework were prepared through simple impregnation followed by calcination. The as-prepared self-supporting electrodes present ultrahigh activity and robust stability. Among them, the NiFeS14@NCNM/CW catalyst yields incredible OER activity with an extraordinarily low overpotential of 147 and 250 mV to reach 10 and 50 mA cm-2, respectively, superior to most of the state-of-the-art wood-derived electrocatalysts. Additionally, a steady OER current density is maintained without obvious attenuation after continuous operation for 24 h. The superior electrocatalytic performance of NiFeS14@NCNM/CW is attributed to the synergistic effect of hybridization between Ni3S2 and Fe5Ni4S8, the coordination of one-dimensional (1D) NCNMs and hierarchical three-dimensional (3D) porous CW, modified electronic states by N and S doping, a large electrochemical surface area, and low activation energy. This research provides a novel approach to industrial-scale conversion of abundant biomass into efficient binder-free electrocatalysts for energy-related applications.

Functional Janus structured liquids and aerogels.

Janus structures have unique properties due to their distinct functionalities on opposing faces, but have yet to be realized with flowing liquids. We demonstrate such Janus liquids with a customizable distribution of nanoparticles (NPs) throughout their structures by joining two aqueous streams of NP dispersions in an apolar liquid. Using this anisotropic integration platform, different magnetic, conductive, or non-responsive NPs can be spatially confined to opposite sides of the original interface using magnetic graphene oxide (mGO)/GO, Ti3C2Tx/GO, or GO suspensions. The resultant Janus liquids can be used as templates for versatile, responsive, and mechanically robust aerogels suitable for piezoresistive sensing, human motion monitoring, and electromagnetic interference (EMI) shielding with a tuned absorption mechanism. The EMI shields outperform their current counterparts in terms of wave absorption, i.e., SET ≈ 51 dB, SER ≈ 0.4 dB, and A = 0.91, due to their high porosity ranging from micro- to macro-scales along with non-interfering magnetic and conductive networks imparted by the Janus architecture.

Stereochemistry-dependent thermotropic liquid crystalline phases of monosaccharide-based amphiphiles.

Conformational rigidity controls the bulk self-assembly and liquid crystallinity from amphiphilic block molecules to copolymers. The effects of block stereochemistry on the self-assembly have, however, been less explored. Here, we have investigated amphiphilic block molecules involving eight open-chain monosaccharide-based polyol units possessing different stereochemistries, derived from D-glucose, D-galactose, L-arabinose, D-mannose and L-rhamnose (allylated monosaccharides t-Glc*, e-Glc*, t-Gal*, e-Gal*, t-Ara*, e-Ara*, t-Man*, and t-Rha*), end-functionalized with repulsive tetradecyl alkyl chain blocks to form well-defined amphiphiles with block molecule structures. All compounds studied showed low temperature crystalline phases due to polyol crystallization, and smectic (lamellar) and isotropic phases upon heating in bulk. Hexagonal cylindrical phase was additionally observed for the composition involving t-Man*. Cubic phases were observed for e-Glc*, e-Gal*, e-Ara*, and t-Rha* derived compounds. Therein, the rich array of WAXS-reflections suggested that the crystalline polyol domains are not ultra-confined in spheres as in classic cubic phases but instead show network-like phase continuity, which is rare in bulk liquid crystals. Importantly, the transition temperatures of the self-assemblies were observed to depend strongly on the polyol stereochemistry. The findings underpin that the stereochemistry in carbohydrate-based assemblies involves complexity, which is an important parameter to be considered in material design when developing self-assemblies for different functions.

Lignin nanoparticles as co-stabilizers and modifiers of nanocellulose-based Pickering emulsions and foams.

Nanocellulose is very hydrophilic, preventing interactions with the oil phase in Pickering emulsions. This limitation is herein addressed by incorporating lignin nanoparticles (LNPs) as co-stabilizers of nanocellulose-based Pickering emulsions. LNP addition decreases the oil droplet size and slows creaming at pH 5 and 8 and with increasing LNP content. Emulsification at pH 3 and LNP cationization lead to droplet flocculation and rapid creaming. LNP application for emulsification, prior or simultaneously with nanocellulose, favors stability given the improved interactions with the oil phase. The Pickering emulsions can be freeze-dried, enabling the recovery of a solid macroporous foam that can act as adsorbent for pharmaceutical pollutants. Overall, the properties of nanocellulose-based Pickering emulsions and foams can be tailored by LNP addition. This strategy offers a unique, green approach to stabilize biphasic systems using bio-based nanomaterials without tedious and costly modification procedures. Supplementary Information: The online version contains supplementary material available at 10.1007/s10570-023-05399-y.