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.

Copper-coordinated cellulose ion conductors for solid-state batteries.

Although solid-state lithium (Li)-metal batteries promise both high energy density and safety, existing solid ion conductors fail to satisfy the rigorous requirements of battery operations. Inorganic ion conductors allow fast ion transport, but their rigid and brittle nature prevents good interfacial contact with electrodes. Conversely, polymer ion conductors that are Li-metal-stable usually provide better interfacial compatibility and mechanical tolerance, but typically suffer from inferior ionic conductivity owing to the coupling of the ion transport with the motion of the polymer chains1-3. Here we report a general strategy for achieving high-performance solid polymer ion conductors by engineering of molecular channels. Through the coordination of copper ions (Cu2+) with one-dimensional cellulose nanofibrils, we show that the opening of molecular channels within the normally ion-insulating cellulose enables rapid transport of Li+ ions along the polymer chains. In addition to high Li+ conductivity (1.5 × 10-3 siemens per centimetre at room temperature along the molecular chain direction), the Cu2+-coordinated cellulose ion conductor also exhibits a high transference number (0.78, compared with 0.2-0.5 in other polymers2) and a wide window of electrochemical stability (0-4.5 volts) that can accommodate both the Li-metal anode and high-voltage cathodes. This one-dimensional ion conductor also allows ion percolation in thick LiFePO4 solid-state cathodes for application in batteries with a high energy density. Furthermore, we have verified the universality of this molecular-channel engineering approach with other polymers and cations, achieving similarly high conductivities, with implications that could go beyond safe, high-performance solid-state batteries.

Molecular mechanisms of self-incompatibility in Brassicaceae and Solanaceae.

Self-incompatibility (SI) is a mechanism for preventing self-fertilization in flowering plants. SI is controlled by a single S-locus with multiple haplotypes (S-haplotypes). When the pistil and pollen share the same S-haplotype, the pollen is recognized as self and rejected by the pistil. This review introduces our research on Brassicaceae and Solanaceae SI systems to identify the S-determinants encoded at the S-locus and uncover the mechanisms of self/nonself-discrimination and pollen rejection. The recognition mechanisms of SI systems differ between these families. A self-recognition system is adopted by Brassicaceae, whereas a collaborative nonself-recognition system is used by Solanaceae. Work by our group and subsequent studies indicate that plants have evolved diverse SI systems.

Rate-Limited Reaction in TEMPO/Laccase/O2 Oxidation of Cellulose.

The environment-friendly oxidation of cellulose by the 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO)/laccase/O2 system is an alternative route with huge potential to prepare cellulose nanofibers. It is found that the concentration of TEMPO significantly affects the oxidation efficiency. An effective method for improving the oxidation effect is to increase the TEMPO concentration and prolong the oxidation time. To clarify the rate-limited step of TEMPO/laccase/O2 oxidation of cellulose, the academically accepted oxidation process is divided into individual pathways. A series of experiments is conducted with laccase and the three forms of organocatalyst (TEMPO, oxoammonium (TEMPO+), and hydroxylamine (TEMPOH)) to simulate individual reactions and calculate the reaction rates. The concentrations of TEMPO and oxoammonium are monitored by EPR spectroscopy. The oxidation rate of TEMPO by laccase varies at different pH conditions, and laccase activity is much higher at pH 4.5. Other reactions without laccase involved express a higher reaction rate when the pH value increased. TEMPO is mainly regenerated through a comproportionation reaction between oxoammonium and hydroxylamine. The acceleration of TEMPO regeneration by laccase is not obvious. The results indicate that the rate-limited reaction in TEMPO/laccase/O2 oxidation is cellulose oxidation by TEMPO+.

A bacterial endo-ß-1,4-glucuronan lyase, CUL-I from Brevundimonas sp. SH203, belonging to a novel polysaccharide lyase family.

Cellouronate is a (1,4)-ß-D-glucuronan prepared by TEMPO-mediated oxidation from regenerated cellulose. We have previously isolated a cellouronate-degrading bacterial strain, Brevundimonas sp. SH203, that produces a cellouronate lyase (ß-1,4-glucuronan lyase, CUL-I). In this study, the gene encoding CUL-I was cloned, and the recombinant enzyme was heterologously expressed in Escherichia coli. The predicted CUL-I protein is composed of 426 amino acid residues and includes a putative 21-amino acid signal peptide. The recombinant CUL-I specifically depolymerized ß-1,4-glycoside linkages of cellouronate, and its mode of action was endo-type, like the native CUL-I. Sequence analysis showed CUL-I has no similarity to previously known polysaccharide lyases (PLs), indicating that CUL-I should be classified into a novel PL family.

Changes to the Contour Length, Molecular Chain Length, and Solid-State Structures of Nanocellulose Resulting from Sonication in Water.

Sonication in water reduced the average contour lengths of nanocellulose prepared from wood cellulose fiber and microcrystalline cellulose. Most of the kinks in the wood cellulose nanofibrils were formed during the initial 10 min of sonication. Fragmentation occurred at the kinks and rigid segments associated with depolymerization during subsequent sonication for 10-120 min, resulting in the formation of cellulose nanocrystals with low aspect ratios. Solid-state cross-polarization magic angle sample spinning 13C-nuclear magnetic resonance revealed that the original crystalline regions of the cellulose were partly transformed to fibril surfaces or disordered regions by both pretreatment and the subsequent fragmentation of molecular chains during sonication. The nanocellulose prepared from microcrystalline cellulose had different fragmentation behavior with regard to molecular chain length following sonication. The results indicated that on average the hexagonal 36 cellulose chain structure formed the cross-section of each wood cellulose microfibril.

Synthesis of Chitin Nanofiber-Coated Polymer Microparticles via Pickering Emulsion.

Chitin nanofiber (ChNF) has received significant research attention owing to its potential for use in a variety of applications, such as medicine and cosmetics. Here, we synthesize a novel ChNF material, ChNF-coated polymer microparticles, using a Pickering emulsion-templated approach. Two varieties of ChNF with different crystal structures, lengths, and surface charges were used to form the microparticle shells. When ChNFs with a shorter length and greater surface charge were used, the microparticles showed good dispersibility in water and narrow size distribution with number- and volume-median diameters of 1.46 and 1.84 µm, respectively. The microparticles were easily collected by filtration and redispersed in water, even after drying. The surface ChNF shells assembled at the microparticle surfaces showed potential as an adsorption site, effectively capturing anionic dye molecules. This technique offers new opportunities for the development of green nanocomposite materials using a facile aqueous process.

Dual Functions of TEMPO-Oxidized Cellulose Nanofibers in Oil-in-Water Emulsions: A Pickering Emulsifier and a Unique Dispersion Stabilizer.

The emulsifying and dispersing mechanisms of oil-in-water emulsions stabilized by 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO)-oxidized cellulose nanofibers (CNFs) have been investigated. The emulsifying mechanism was studied by changing the oil/water interfacial tension from 8.5 to 53.3 mN/m using various types of oils. The results showed that the higher the oil/water interfacial tension, the greater is the amount of CNFs adsorbed at the oil/water interface, making the CNF-adsorbed oil-in-water emulsions thermodynamically more stable. Moreover, the amount of CNFs adsorbed on the surfaces of the oil droplets increased with increasing interfacial area. The dispersion stability of the oil droplets was dominated by the CNF concentration in the water phase. Above the critical concentration (0.15% w/w), the CNFs formed network structures in the water phase, and the emulsion was effectively stabilized against creaming. Emulsion formation and the CNF network structures in the emulsion were visualized by cryo-scanning electron microscopy.

Dual Counterion Systems of Carboxylated Nanocellulose Films with Tunable Mechanical, Hydrophilic, and Gas-Barrier Properties.

Aqueous dispersions of C6-carboxylated cellulose nanofibrils with sodium counterions (CNF-COONa) and CNFs with tetraethylammonium counterions (CNF-COONEt4) were mixed at various weight ratios. Transparent, flexible CNF-COONa/NEt4 films were prepared by casting and drying aqueous mixtures with various Na/NEt4 molar ratios as dual counterion systems. The film density, Young's modulus, and tensile strength decreased linearly with increasing molar ratio of the bulky NEt4 counterion. The film hydrophilicity was controlled by varying the Na/NEt4 molar ratio. The oxygen and water vapor permeabilities also increased with increasing molar ratio of bulky NEt4 counterions. The mechanical, hydrophilic, and gas-barrier properties were tuned by controlling the Na/NEt4 molar ratios of CNF films containing dual counterions. The results of model experiments using tetra( n-butyl)ammonium hydroxide indicated that the Na and quaternary alkylammonium counterions were homogeneously distributed among the carboxylated CNF elements in both dispersions and cast-dried films of the dual counterion systems.

Relationship of Distribution of Carboxy Groups to Molar Mass Distribution of TEMPO-Oxidized Algal, Cotton, and Wood Cellulose Nanofibrils.

Distributions of carboxy groups among the molecules in 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized cellulose nanofibrils (TOCNs) prepared from wood, cotton, and algal celluloses were investigated. Most C6-carboxy groups in TOCNs were esterified with anthracene-methyl (-CH2C14H9) groups, showing an ultraviolet light (UV) absorption peak at 365 nm. The anthracene-methylated TOCNs were dissolved in 8% (w/w) lithium chloride/N,N-dimethylacetamide (LiCl/DMAc). After dilution to 1% LiCl/DMAc, the solutions were subjected to size-exclusion chromatography with multiangle laser-light scattering, refractive index, and UV detection. For algal TOCN, C6-carboxy group-rich molecules were present predominantly in the low-molar-mass region, which was consistent with the core-clad cellulose chain packing structures in individual algal cellulose microfibrils and partial depolymerization of the oxidized cellulose molecules. In contrast, wood and cotton TOCNs had almost homogeneous distributions of C6-carboxy groups in all molar mass regions, which could not be explained in terms of the simple core-clad cellulose chain packing structures.

Characterization of Concentration-Dependent Gelation Behavior of Aqueous 2,2,6,6-Tetramethylpiperidine-1-oxyl-Cellulose Nanocrystal Dispersions Using Dynamic Light Scattering.

Cellulose nanofibrils (CNFs) and cellulose nanocrystals (CNCs) with high and low aspect ratios, respectively, were prepared from wood cellulose by catalytic oxidation with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and subsequent sonication in water. Cavitation-induced force was used to prepare TEMPO-CNCs from aqueous suspensions of TEMPO-oxidized celluloses. Aqueous dispersions of the TEMPO-CNF and TEMPO-CNCs with different solid concentrations were prepared by dilution or condensation. Dynamic light scattering (DLS) was used to determine the solid concentrations at the transition points from the dilute to semidilute regions and from the semidilute to dense gel regions in the aqueous TEMPO-CNF and TEMPO-CNC dispersions. All the DLS data corresponded well to the fitting curves of the normalized time-correlation functions. The solid concentration at the gelation point increased from 0.40% w/v for the TEMPO-CNF dispersions to 1.71% w/v for the TEMPO-CNC dispersions, and the aspect ratio decreased from 134 to 57, respectively. The solid concentrations of the TEMPO-CNF and TEMPO-CNC dispersions at the gelation point calculated using effective-medium theory based on their aspect ratios corresponded well with those experimentally determined by DLS.

Acid-Free Preparation of Cellulose Nanocrystals by TEMPO Oxidation and Subsequent Cavitation.

Softwood bleached kraft pulp (SBKP) and microcrystalline cellulose (MCC) were oxidized using a 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated system. The TEMPO-oxidized SBKP prepared with 10 mmol/g NaClO (SBKP-10) had a higher mass recovery ratio and higher carboxylate content than the other prepared celluloses including the TEMPO-oxidized MCCs. The SBKP-10 was then exposed to cavitation-induced forces through sonication in water for 10-120 min to prepare aqueous dispersions of needle-like TEMPO-oxidized cellulose nanocrystals (TEMPO-CNCs) with homogeneous width of 3.5 to 3.6 nm and average lengths of ∼200 nm. The average chain lengths of the cellulose molecules that make up the TEMPO-CNCs were less than half the average lengths of the TEMPO-CNCs. Compared with conventional CNCs prepared by acid hydrolysis, the TEMPO-CNCs prepared by the acid-free and dialysis-free process exhibited higher mass recovery ratios, significantly higher amounts of surface anionic groups, and smaller and more homogeneous widths.

Development of completely dispersed cellulose nanofibers.

Plant cellulose fibers of width and length ∼0.03 mm and ∼3 mm, respectively, can be completely converted to individual cellulose nanofibers of width and length ∼3 nm and ∼1 µm, respectively, by 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-mediated oxidation under aqueous conditions and subsequent gentle mechanical disintegration of the oxidized cellulose in water. The obtained TEMPO-oxidized cellulose nanofibers (TOCNs) are new bio-based, crystalline nanomaterials with applications in the high-tech and commodity product industries. Sodium carboxylate groups, which are densely, regularly, and position-selectively present on the crystalline TOCN surfaces, can be efficiently ion-exchanged with other metal and alkylammonium carboxylate groups in water to control the biodegradable/stable and hydrophilic/hydrophobic properties of the TOCNs. TOCNs are therefore promising nanomaterials that can be prepared from the abundant wood biomass resources present in Japan. Increased production and use of TOCNs would stimulate a new material stream from forestry to industries, helping to establish a sustainable society based on wood biomass resources.

Molar Masses and Molar Mass Distributions of Chitin and Acid-Hydrolyzed Chitin.

Never-dried and dried crab shell chitin and squid pen chitin samples were acid-hydrolyzed in 1 M HCl at 85 °C for up to 2 h. The crystallinities, crystal sizes, and degrees of N-acetylation of the acid-hydrolyzed chitin samples are almost unchanged the same before and after acid hydrolysis. The original and acid-hydrolyzed chitin samples were dissolved in 8% (w/w) lithium chloride/N,N,-dimethylacetamide, and the solutions were subjected to size-exclusion chromatography with multiangle laser-light scattering analysis to determine their molar masses and molar mass distributions. The molar mass of each chitin sample decreases with increasing acid hydrolysis time, and the weight-average degree of polymerization (DPw) becomes constant after acid hydrolysis for 0.5 to 2 h. However, the DPw values of the chitin samples after acid hydrolysis for 2 h (DPw-2h) are different: Never-dried squid pen chitin has the highest DPw-2h of 1530, whereas the DPw-2h values of other chitin samples are in the range 220-410.

Estimating the Strength of Single Chitin Nanofibrils via Sonication-Induced Fragmentation.

We report the mechanical strength of native chitin nanofibrils. Highly crystalline α-chitin nanofibrils were purified from filaments produced by a microalgae Phaeocystis globosa, and two types of ß-chitin nanofibrils were purified from pens of a squid Loligo bleekeri and tubes of a tubeworm Lamellibrachia satsuma, with relatively low and high crystallinity, respectively. These chitin nanofibrils were fully dispersed in water. The strength of individualized nanofibrils was estimated using cavitation-induced tensile fracture of nanoscale filaments in a liquid medium. Both types of ß-chitin nanofibrils exhibited similar strength values of approximately 3 GP; in contrast, the α-chitin nanofibrils exhibited a much lower strength value of 1.6 GPa. These strength estimates suggest that the tensile strength of chitin nanofibrils is governed by the molecular packing modes of chitin rather than their crystallinity.

Dynamic Viscoelastic Functions of Liquid-Crystalline Chitin Nanofibril Dispersions.

The dynamic viscoelastic functions of aqueous chitin nanofibril (ChNF) dispersions are defined by their liquid-crystalline fibril arrangement. Four ChNF dispersions with different structures were prepared from squid-pen ß-chitin, by sonication in aqueous acetic acid at pH 3 for 4-40 min. Squid-pen ß-chitin was disintegrated into randomly oriented bundles of ChNFs during the initial stage of sonication and then became more finely dispersed with further sonication up to 8 min. The additional sonication resulted in the individualization of the approximately 3 nm-wide ChNFs. The individual ChNFs self-organized into a nematic liquid crystalline phase. All ChNF dispersions showed power-law concentration c dependences of their storage moduli G' at a certain angular frequency ω (Gω' = Acα). The front factor A was positively correlated with the degree of disintegration. The exponent α increased from 2.7 to 3.8-3.9, as the ChNF dispersion self-organized from the randomly dispersed structure into the nematic-ordered fibril arrangement. This demonstrated an enhancement in the solid concentration dependence.

Different Conformations of Surface Cellulose Molecules in Native Cellulose Microfibrils Revealed by Layer-by-Layer Peeling.

Layer-by-layer peeling of surface molecules of native cellulose microfibrils was performed using a repeated sequential process of 2,2,6,6-tetramethylpiperidine-1-oxyl radical-mediated oxidation followed by hot alkali extraction. Both highly crystalline algal and tunicate celluloses and low-crystalline cotton and wood celluloses were investigated. Initially, the C6-hydroxy groups of the outermost surface molecules of each algal cellulose microfibril facing the exterior had the gauche-gauche (gg) conformation, whereas those facing the interior had the gauche-trans (gt) conformation. All the other C6-hydroxy groups of the cellulose molecules inside the microfibrils contributing to crystalline cellulose I had the trans-gauche (tg) conformation. After surface peeling, the originally second-layer molecules from the microfibril surface became the outermost surface molecules, and the original tg conformation changed to gg and gt conformations. The plant cellulose microfibrils likely had disordered structures for both the outermost surface and second-layer molecules, as demonstrated using the same layer-by-layer peeling technique.

Cellulose Nanofibers Prepared Using the TEMPO/Laccase/O2 System.

The 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)/laccase/O2 system was used to prepare cellulose nanofibers from wood cellulose without requiring any chlorine-containing oxidant. Laccase was degraded by oxidized TEMPO (TEMPO+) formed by laccase-mediated oxidation with O2, which competed with the oxidation of wood cellulose. Thus, large amounts of laccase and TEMPO and a long reaction time were needed to introduce ∼0.6 mmol g-1 of C6-carboxylate groups onto wood cellulose. The TEMPO/laccase/O2 system underwent one-way reaction from TEMPO to reduced TEMPO through TEMPO+. When the oxidation was applied again to the oxidized wood cellulose following isolation and purification, the C6-carboxylate groups increased to ∼1.1 mmol g-1, which was sufficient to convert the sample to cellulose nanofibers by sonication in water. However, the higher the carboxylate content of the oxidized celluloses, the lower their degree of polymerization.

Reliable dn/dc Values of Cellulose, Chitin, and Cellulose Triacetate Dissolved in LiCl/N,N-Dimethylacetamide for Molecular Mass Analysis.

Freeze-dried microfibrillated cellulose (MFC) was directly dissolved in 8.0% w/w lithium chloride/N,N-dimethylacetamide (LiCl/DMAc), and MFC/LiCl/DMAc solutions with accurate MFC concentrations were prepared. The different MFC solutions were diluted to 1.0% and 0.5% w/v LiCl/DMAc, and subjected to size-exclusion chromatography with multiangle laser-light scattering and refractive index analyses (SEC/MALLS/RI), and off-line RI analysis to determine their refractive index increments (dn/dc). Chitin, cellulose triacetate, a poly(styrene) standard, and cellobiose were used for comparison. Each of the two determination methods gave different dn/dc values for MFC and chitin but similar dn/dc values for cellulose triacetate and poly(styrene). The anomalously small dn/dc values of MFC and chitin were explainable in terms of stable cellulose-LiCl and chitin-LiCl structures (i.e., formation of apparent covalent bonds between hydroxyl groups and LiCl) in the solutions. Thus, the SEC/MALLS/RI method provides reliable molecular mass parameters for cellulose and chitin.

Viscoelastic Properties of Core-Shell-Structured, Hemicellulose-Rich Nanofibrillated Cellulose in Dispersion and Wet-Film States.

We report the viscoelastic properties of core-shell-structured, hemicellulose-rich nanofibrillated cellulose (NFC) in dispersion and wet-film states. The hemicellulose-rich NFC (hemicellulose neutral sugars 23%, carboxylate 0.2 mmol g(-1)), prepared from Japanese persimmons, had a core crystallite thickness of 2.3 nm and unit fibril thickness of 4.2 nm. A carboxylate-rich NFC (hemicellulose neutral sugars 7%, carboxylate 0.9 mmol g(-1)) with crystallite and fibril widths of 2.5 and 3.3 nm, respectively, was used as a reference. The solid-concentration dependencies of the storage moduli of gel-like water dispersions of the hemicellulose-rich NFC were weaker than those of carboxylate-rich NFC, and the dispersions were loosely flocculated even at high salt concentrations and low pH values. The viscoelastic properties of wet NFC films were similar to those of their dispersions; the hemicellulose-rich NFC films were significantly less sensitive to salt concentration and pH and were soft and swollen at high salt concentrations and low pH values.