Developing fibrillated cellulose as a sustainable technological material.

Cellulose is the most abundant biopolymer on Earth, found in trees, waste from agricultural crops and other biomass. The fibres that comprise cellulose can be broken down into building blocks, known as fibrillated cellulose, of varying, controllable dimensions that extend to the nanoscale. Fibrillated cellulose is harvested from renewable resources, so its sustainability potential combined with its other functional properties (mechanical, optical, thermal and fluidic, for example) gives this nanomaterial unique technological appeal. Here we explore the use of fibrillated cellulose in the fabrication of materials ranging from composites and macrofibres, to thin films, porous membranes and gels. We discuss research directions for the practical exploitation of these structures and the remaining challenges to overcome before fibrillated cellulose materials can reach their full potential. Finally, we highlight some key issues towards successful manufacturing scale-up of this family of materials.

Topological superconductivity in a van der Waals heterostructure.

Exotic states such as topological insulators, superconductors and quantum spin liquids are often challenging or impossible to create in a single material1-3. For example, it is unclear whether topological superconductivity, which has been suggested to be a key ingredient for topological quantum computing, exists in any naturally occurring material4-9. The problem can be circumvented by deliberately selecting the combination of materials in heterostructures so that the desired physics emerges from interactions between the different components1,10-15. Here we use this designer approach to fabricate van der Waals heterostructures that combine a two-dimensional (2D) ferromagnet with a superconductor, and we observe 2D topological superconductivity in the system. We use molecular-beam epitaxy to grow 2D islands of ferromagnetic chromium tribromide16 on superconducting niobium diselenide. We then use low-temperature scanning tunnelling microscopy and spectroscopy to reveal the signatures of one-dimensional Majorana edge modes. The fabricated 2D van der Waals heterostructure provides a high-quality, tunable system that can be readily integrated into device structures that use topological superconductivity. The layered heterostructures can be readily accessed by various external stimuli, potentially allowing external control of 2D topological superconductivity through electrical17, mechanical18, chemical19 or optical means20.

Biofabrication with microbial cellulose: from bioadaptive designs to living materials.

Nanocellulose is not only a renewable material but also brings functions that are opening new technological opportunities. Here we discuss a special subset of this material, in its fibrillated form, which is produced by aerobic microorganisms, namely, bacterial nanocellulose (BNC). BNC offers distinct advantages over plant-derived counterparts, including high purity and high degree of polymerization as well as crystallinity, strength, and water-holding capacity, among others. More remarkably, beyond classical fermentative protocols, it is possible to grow BNC on non-planar interfaces, opening new possibilities in the assembly of advanced bottom-up structures. In this review, we discuss the recent advances in the area of BNC-based biofabrication of three-dimensional (3D) designs by following solid- and soft-material templating. These methods are shown as suitable platforms to achieve bioadaptive constructs comprising highly interlocked biofilms that can be tailored with precise control over nanoscale morphological features. BNC-based biofabrication opens applications that are not possible by using traditional manufacturing routes, including direct ink writing of hydrogels. This review emphasizes the critical contributions of microbiology, colloid and surface science, as well as additive manufacturing in achieving bioadaptive designs from living matter. The future impact of BNC biofabrication is expected to take advantage of material and energy integration, residue utilization, circularity and social latitudes. Leveraging existing infrastructure, the scaleup of biofabrication routes will contribute to a new generation of advanced materials rooted in exciting synergies that combine biology, chemistry, engineering and material sciences.

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.

Recent Progress in MOF-Aerogel Fabrication and Applications.

Recent advancements in metal-organic frameworks (MOFs) underscore their significant potential in chemical and materials research, owing to their remarkable properties and diverse structures. Despite challenges like intrinsic brittleness, powdered crystalline nature, and limited stability impeding direct applications, MOF-based aerogels have shown superior performance in various areas, particularly in water treatment and contaminant removal. This review highlights the latest progress in MOF-based aerogels, with a focus on hybrid systems incorporating materials like graphene, carbon nanotube, silica, and cellulose in MOF aerogels, which enhance their functional properties. The manifold advantages of MOF-based aerogels in energy storage, adsorption, and catalysis are discussed, with an emphasizing on their improved stability, processability, and ease of handling. This review aims to unlock the potential of MOF-based aerogels and their real-world applications. Aerogels are expected to reshape the technological landscape of MOFs through enhanced stability, adaptability, and efficiency.

Interfacial Membranization of Regenerated Cellulose Nanoparticles and a Protein Renders Stable Water-in-Water Emulsion.

Pickering water-in-water (W/W) emulsions stabilized by biobased colloids are pertinent to engineering biomaterials with hierarchical and confined architectures. In this study, stable W/W emulsions are developed through membranization utilizing biopolymer structures formed by the adsorption of cellulose II nanospheres and a globular protein, bovine serum albumin (BSA), at droplet surfaces. The produced cellulose II nanospheres (NPcat, 63 nm diameter) bearing a soft and highly accessible shell, endow rapid and significant binding (16 mg cm- 2) with BSA. NPcat and BSA formed complexes that spontaneously stabilized liquid droplets, resulting in stable W/W emulsions. It is proposed that such a system is a versatile all-aqueous platform for encapsulation, (bio)catalysis, delivery, and synthetic cell mimetics.

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.

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.

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.

Nanochitin: Chemistry, Structure, Assembly, and Applications.

Chitin, a fascinating biopolymer found in living organisms, fulfills current demands of availability, sustainability, biocompatibility, biodegradability, functionality, and renewability. A feature of chitin is its ability to structure into hierarchical assemblies, spanning the nano- and macroscales, imparting toughness and resistance (chemical, biological, among others) to multicomponent materials as well as adding adaptability, tunability, and versatility. Retaining the inherent structural characteristics of chitin and its colloidal features in dispersed media has been central to its use, considering it as a building block for the construction of emerging materials. Top-down chitin designs have been reported and differentiate from the traditional molecular-level, bottom-up synthesis and assembly for material development. Such topics are the focus of this Review, which also covers the origins and biological characteristics of chitin and their influence on the morphological and physical-chemical properties. We discuss recent achievements in the isolation, deconstruction, and fractionation of chitin nanostructures of varying axial aspects (nanofibrils and nanorods) along with methods for their modification and assembly into functional materials. We highlight the role of nanochitin in its native architecture and as a component of materials subjected to multiscale interactions, leading to highly dynamic and functional structures. We introduce the most recent advances in the applications of nanochitin-derived materials and industrialization efforts, following green manufacturing principles. Finally, we offer a critical perspective about the adoption of nanochitin in the context of advanced, sustainable materials.

On-Surface Synthesis of Silole and Disila-Cyclooctene Derivatives.

The incorporation of Si atoms into organic compounds significantly increases a variety of functionality, facilitating further applications. Recently, on-surface synthesis was introduced into organosilicon chemistry as 1,4-disilabenzene bridged nanostructures were obtained via coupling between silicon atoms and brominated phenyl groups at the ortho position on Au(111). Here, we demonstrate a high generality of this strategy via syntheses of silole derivatives and nanoribbon structures with eight-membered sila-cyclic rings from dibrominated molecules at the bay and peri positions on Au(111), respectively. Their structures and electronic properties were investigated by a combination of scanning tunneling microscopy/spectroscopy and density functional theory calculations. This work demonstrates a great potential to deal with heavy group 14 elements in on-surface silicon chemistry.

Novel Benchmark Values for Open Major Anatomic Liver Resection in Non-cirrhotic Patients: A Multicentric Study of 44 International Expert Centers.

OBJECTIVE: This study aims at establishing benchmark values for best achievable outcomes following open major anatomic hepatectomy for liver tumors of all dignities. BACKGROUND: Outcomes after open major hepatectomies vary widely lacking reference values for comparisons among centers, indications, types of resections, and minimally invasive procedures. METHODS: A standard benchmark methodology was used covering consecutive patients, who underwent open major anatomic hepatectomy from 44 high-volume liver centers from 5 continents over a 5-year period (2016-2020). Benchmark cases were low-risk non-cirrhotic patients without significant comorbidities treated in high-volume centers (≥30 major liver resections/year). Benchmark values were set at the 75th percentile of median values of all centers. Minimum follow-up period was 1 year in each patient. RESULTS: Of 8044 patients, 2908 (36%) qualified as benchmark (low-risk) cases. Benchmark cutoffs for all indications include R0 resection ≥78%; liver failure (grade B/C) ≤10%; bile leak (grade B/C) ≤18%; complications ≥grade 3 and CCI ® ≤46% and ≤9 at 3 months, respectively. Benchmark values differed significantly between malignant and benign conditions so that reference values must be adjusted accordingly. Extended right hepatectomy (H1, 4-8 or H4-8) disclosed a higher cutoff for liver failure, while extended left (H1-5,8 or H2-5,8) were associated with higher cutoffs for bile leaks, but had superior oncologic outcomes, when compared to formal left hepatectomy (H1-4 or H2-4). The minimal follow-up for a conclusive outcome evaluation following open anatomic major resection must be 3 months. CONCLUSION: These new benchmark cutoffs for open major hepatectomy provide a powerful tool to convincingly evaluate other approaches including parenchymal-sparing procedures, laparoscopic/robotic approaches, and alternative treatments, such as ablation therapy, irradiation, or novel chemotherapy regimens.

Insulative Biobased Glaze from Wood Laminates Obtained by Self-Adhesion.

The combination of optical transparency and mechanical strength is a highly desirable attribute of wood-based glazing materials. However, such properties are typically obtained by impregnation of the highly anisotropic wood with index-matching fossil-based polymers. In addition, the presence of hydrophilic cellulose leads to a limited water resistance. Herein, this work reports on an adhesive-free lamination that uses oxidation and densification to produce transparent all-biobased glazes. The latter are produced from multilayered structures, free of adhesives or filling polymers, simultaneously displaying high optical clarity and mechanical strength, in both dry and wet conditions. Specifically, high values of optical transmittance (≈85.4%), clarity (≈20% with low haze) at a thickness of ≈0.3 mm, and highly isotropic mechanical strength and water resistance (wet strength of ≈128.25 MPa) are obtained for insulative glazes exhibiting low thermal conductivity (0.27 W m-1 K-1 , almost four times lower than glass). The proposed strategy results in materials that are systematically tested, with the leading effects of self-adhesion induced by oxidation rationalized by ab initio molecular dynamics simulation. Overall, this work demonstrates wood-derived materials as promising solutions for energy-efficient and sustainable glazing applications.

Super-Macroporous Lightweight Materials Templated from Bicontinuous Intra-Phase Jammed Emulsion Gels Based on Nanochitin.

Non-equilibrium multiphase systems are formed by mixing two immiscible nanoparticle dispersions, leading to bicontinuous emulsions that template cryogels with interconnected, tortuous channels. Herein, a renewable, rod-like biocolloid (chitin nanocrystals, ChNC) is used to kinetically arrest bicontinuous morphologies. Specifically, it is found that ChNC stabilizes intra-phase jammed bicontinuous systems at an ultra-low particle concentration (as low as 0.6 wt.%), leading to tailorable morphologies. The synergistic effects of ChNC high aspect ratio, intrinsic stiffness, and interparticle interactions produce hydrogelation and, upon drying, lead to open channels bearing dual characteristic sizes, suitably integrated into robust bicontinuous ultra-lightweight solids. Overall, it demonstrates the successful formation of ChNC-jammed bicontinuous emulsions and a facile emulsion templating route to synthesize chitin cryogels that form unique super-macroporous networks.

Mapping 3D Printability of Ionically Cross-Linked Cellulose Nanocrystal Inks: Architecting from Nano- to Macroscale Structures.

Engineering the rheological properties of colloidal inks is one of the main challenges in achieving high-fidelity 3D printing. Herein, we provide a comprehensive study on the rheological behavior of inks based on cellulose nanocrystals (CNCs) in the presence of given salts to enable high-quality 3D printing. The rheological properties of the CNC suspensions are tailored by considering the nature of the electrolyte (i.e., 10 types of salts featuring different ion sizes, charge numbers, and inter- and intra-molecular interactions) at various concentrations (25-100 mM). A high printing fidelity is achieved in a narrow CNC and salt concentration range, significantly depending on the salt type. The structure-property relationship is explored in a "3D-printing" space (2D map), introducing a guideline for researchers active in this field. To further unravel the effect of salt type on morphological properties, CNC aerogels are developed by freeze-drying the printed structures. The results illustrate that enhancing viscoelastic properties render a denser structure featuring smaller pores.

Formation and Identification of Lignin-Carbohydrate Complexes in Pre-hydrolysis Liquors.

The lignin-carbohydrate complexes (LCCs) typically present in the liquors produced in the pre-hydrolysis of biomass cause severe difficulties in downstream fractionation. To address this issue, a series of LCC samples were accessed from solutions obtained from the pre-hydrolysis of extractive-free pine wood meal (H-LCC) and compared with LCC obtained from the corresponding residues (B-LCC). Chromatographic and spectroscopic techniques revealed that 8.2% of the lignins were degraded at 160 °C, resulting from the breakage of ß-O-4' linkages during pre-hydrolysis. Meanwhile, (reactive) hemicelluloses were mainly removed from the fibers' cell walls. Some hemicelluloses in the pre-hydrolysis liquor, such as glucomannans, were associated with degraded lignin fragments via ether and ester bonds. However, the newly formed LCCs were pH-labile and underwent rapid hydrolysis. Overall, we reveal details about LCC formation and degradation during pre-hydrolysis at given temperatures, critically important in efforts to improve biomass processing and valorization.

All-Aqueous Bicontinuous Structured Liquid Crystal Emulsion through Intraphase Trapping of Cellulose Nanoparticles.

Here, we describe the all-aqueous bicontinuous emulsions with cholesteric liquid crystal domains through hierarchical colloidal self-assembly of nanoparticles. This is achieved by homogenization of a rod-like cellulose nanocrystal (CNC) with two immiscible, phase separating polyethylene glycol (PEG) and dextran polymer solutions. The dispersed CNCs exhibit unequal affinity for the binary polymer mixtures that depends on the balance of osmotic and chemical potential between the two phases. Once at the critical concentration, CNC particles are constrained within one component of the polymer phases and self-assemble into a cholesteric organization. The obtained liquid crystal emulsion demonstrates a confined three-dimensional percolating bicontinuous network with cholesteric self-assembly of CNC within the PEG phase; meanwhile, the nanoparticles in the dextran phase remain isotropic instead. Our results provide an alternative way to arrest bicontinuous structures through intraphase trapping and assembling of nanoparticles, which is a viable and flexible route to extend for a wide range of colloidal systems.

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.

Deconstruction and Reassembly of Renewable Polymers and Biocolloids into Next Generation Structured Materials.

This review considers the most recent developments in supramolecular and supraparticle structures obtained from natural, renewable biopolymers as well as their disassembly and reassembly into engineered materials. We introduce the main interactions that control bottom-up synthesis and top-down design at different length scales, highlighting the promise of natural biopolymers and associated building blocks. The latter have become main actors in the recent surge of the scientific and patent literature related to the subject. Such developments make prominent use of multicomponent and hierarchical polymeric assemblies and structures that contain polysaccharides (cellulose, chitin, and others), polyphenols (lignins, tannins), and proteins (soy, whey, silk, and other proteins). We offer a comprehensive discussion about the interactions that exist in their native architectures (including multicomponent and composite forms), the chemical modification of polysaccharides and their deconstruction into high axial aspect nanofibers and nanorods. We reflect on the availability and suitability of the latter types of building blocks to enable superstructures and colloidal associations. As far as processing, we describe the most relevant transitions, from the solution to the gel state and the routes that can be used to arrive to consolidated materials with prescribed properties. We highlight the implementation of supramolecular and superstructures in different technological fields that exploit the synergies exhibited by renewable polymers and biocolloids integrated in structured materials.

Immobilized cellulose nanospheres enable rapid antigen detection in lateral flow immunoassays.

Rapid diagnostic systems are essential in controlling the spread of viral pathogens and efficient patient management. The available technologies for low-cost viral antigen testing have several limitations, including a lack of accuracy and sensitivity. Here, we introduce a platform based on cellulose II nanoparticles (oppositely charged NPan and NPcat) for effective control of surface protein interactions, leading to rapid and sensitive antigen tests. Passivation against non-specific adsorption and augmented immobilization of sensing antibodies is achieved by adjusting the electrostatic charge of the nanoparticles. The interactions affecting the performance of the system are investigated by microgravimetry and confocal imaging. As a proof-of-concept test, SARS-CoV-2 nucleocapsid sensing was carried out by using saliva-wicking by channels that were stencil-printed on paper. We conclude that inkjet-printed NPcat elicits strong optical signals, visible after a few minutes, opening the opportunity for cost-effective and rapid diagnostic. Supplementary Information: The online version contains supplementary material available at 10.1007/s10570-022-05038-y.