Aerogels with 3D Ordered Nanofiber Skeletons of Liquid‐Crystalline Nanocellulose Derivatives as Tough and Transparent Insulators

Aerogels of high porosity and with a large internal surface area exhibit outstanding performances as thermal, acoustic, or electrical insulators. However, most aerogels are mechanically brittle and optically opaque, and the structural and physical properties of aerogels strongly depend on their densities. The unfavorable characteristics of aerogels are intrinsic to their skeletal structures consisting of randomly interconnected spherical nanoparticles. A structurally new type of aerogel with a three‐dimensionally ordered nanofiber skeleton of liquid‐crystalline nanocellulose (LC‐NCell) is now reported. This LC‐NCell material is composed of mechanically strong, surface‐carboxylated cellulose nanofibers dispersed in a nematic LC order. The LC‐NCell aerogels are transparent and combine mechanical toughness and good insulation properties. These properties of the LC‐NCell aerogels could also be readily controlled.     

Bioinspired Mechanical Gradients in Cellulose Nanofibril/Polymer Nanopapers

Mechanical gradients are important as tough joints, for strain field engineering in printable electronics, for actuators, and for biological studies, yet they are difficult to prepare and quantitatively characterize. We demonstrate the additive fabrication of gradient bioinspired nanocomposites based on stiff, renewable cellulose nanofibrils that are bottom‐up toughened via a tailor‐made copolymer. Direct filament writing of different nanocomposite hydrogels in patterns, and subsequent healing of the filaments into continuous films while drying leads to a variety of linear, parabolic and striped bulk gradients. In situ digital image correlation under tensile deformation reveals important differences in the strain fields regarding asymmetry and step heights of the patterns. We envisage that merging top‐down and bottom‐up structuring of nanocellulose hybrids opens avenues for aperiodic and multiscale, bioinspired nanocomposites with optimized combinations of stiffness and toughness.     

Improved Hydrophobicity of Macroalgae Biopolymer Film Incorporated with Kenaf Derived CNF Using Silane Coupling Agent

Hydrophilic behaviour of carrageenan macroalgae biopolymer, due to hydroxyl groups, has limited its applications, especially for packaging. In this study, macroalgae were reinforced with cellulose nanofibrils (CNFs) isolated from kenaf bast fibres. The macroalgae CNF film was after that treated with silane for hydrophobicity enhancement. The wettability and functional properties of unmodified macroalgae CNF films were compared with silane-modified macroalgae CNF films. Characterisation of the unmodified and modified biopolymers films was investigated. The atomic force microscope (AFM), SEM morphology, tensile properties, water contact angle, and thermal behaviour of the biofilms showed that the incorporation of Kenaf bast CNF remarkably increased the strength, moisture resistance, and thermal stability of the macroalgae biopolymer films. Moreover, the films’ modification using a silane coupling agent further enhanced the strength and thermal stability of the films apart from improved water-resistance of the biopolymer films compared to unmodified films. The morphology and AFM showed good interfacial interaction of the components of the biopolymer films. The modified biopolymer films exhibited significantly improved hydrophobic properties compared to the unmodified films due to the enhanced dispersion resulting from the silane treatment. The improved biopolymer films can potentially be utilised as packaging materials.     

Hybrid Supramolecular and Colloidal Hydrogels that Bridge Multiple Length Scales

Hybrid nanocomposites were constructed based on colloidal nanofibrillar hydrogels with interpenetrating supramolecular hydrogels, displaying enhanced rheological yield strain and a synergistic improvement in storage modulus. The supramolecular hydrogel consists of naphthyl‐functionalized hydroxyethyl cellulose and a cationic polystyrene derivative decorated with methylviologen moieties, physically cross‐linked with cucurbit[8]uril macrocyclic hosts. Fast exchange kinetics within the supramolecular system are enabled by reversible cross‐linking through the binding of the naphthyl and viologen guests. The colloidal hydrogel consists of nanofibrillated cellulose that combines a mechanically strong nanofiber skeleton with a lateral fibrillar diameter of a few nanometers. The two networks interact through hydroxyethyl cellulose adsorption to the nanofibrillated cellulose surfaces. This work shows methods to bridge the length scales of molecular and colloidal hybrid hydrogels, resulting in synergy between reinforcement and dynamics.     

纳米纤维素/还原氧化石墨烯复合材料用于高性能超级电容器

以高浓度氧化石墨烯(GO)溶液作为反应前驱体,纳米纤维素(NC)作为物理间隔物和电解液储存器,通过简单的一步水热法制备了纳米纤维素/还原氧化石墨烯(NC/rGO)复合材料,并探究了其作为超级电容器电极材料的潜力。结果如下：NC添加量为1 mL所制备的NC/rGO-1具有最佳电化学性能。基于NC/rGO-1的无黏合剂对称型超级电容器在0.3 A·g^-1的电流密度下显示出了 269.33 F·g^-1和 350.13 F·cm^-3的高质量和体积比电容,并在 10.0 A·g^-1时仍能达到 215.88 F·g^-1和 280.62 F·cm^-3(其初始值的 80.15%)。组装器件还显示出了较高的质量和体积能量密度(9.3 Wh·kg^-1和 12.13 Wh·L^-1)和出色的循环性能(10 A·g^-1下10 000次循环后其初始比电容仅减少6.02%)。     

Cellulose Nanocrystals (CNCs) Induced Crystallization of Polyvinyl Alcohol (PVA) Super Performing Nanocomposite Films

This study is aimed to explore the properties of cellulose nanocrystals (CNC)/polyvinyl alcohol (PVA) composite films with and without 1,2,3,4‐butane tetracarboxylic acid (BTCA), a nontoxic crosslinker. CNC and CNC‐PVA nanocomposite films are prepared using solution‐casting technique. Differential scanning calorimetry (DSC) analyses show that crosslinking increased the glass transition temperature but reduced the melting temperature and crystallinity. Furthermore, high CNC concentrations in the PVA matrix interfere with PVA crystallinity, whereas in specific ratio between CNC and PVA, two different crystalline structures are observed within the PVA matrix. Film surfaces and fracture topographies characterized using scanning electron microscope indicate that at certain CNC‐PVA ratios, micron‐sized needle‐like crystals have formed. These crystalline structures correlate with the remarkable improvement in mechanical properties of the CNC‐PVA nanocomposite films, that is, enhanced tensile strain and toughness to 570% and 202 MJ m^?3, respectively, as compared to pristine PVA. BTCA enhances the tensile strain, ultimate tensile stress, toughness, and modulus of CNC films compared to pristine CNC films. Water absorption of crosslinked CNC and CNC‐PVA nanocomposite films is significantly reduced, while film transparency is significantly improved as a function of PVA and crosslinker content. The presented results indicate that CNC‐PVA nanocomposite films may find applications in packaging, and though materials applications.     

In situ Study Unravels Bio‐Nanomechanical Behavior in a Magnetic Bacterial Nano‐cellulose (MBNC) Hydrogel for Neuro‐Endovascular Reconstruction

Surgical clipping and endovascular coiling are well recognized as conventional treatments of Penetrating Brain Injury aneurysms. These clinical approaches show partial success, but often result in thrombus formation and the rupture of aneurysm near arterial walls. The authors address these challenging brain traumas with a unique combination of a highly biocompatible biopolymer hydrogel rendered magnetic in a flexible and resilient membrane coating integrated to a scaffold stent platform at the aneurysm neck orifice, which enhances the revascularization modality. This work focuses on the in situ diagnosis of nano‐mechanical behavior of bacterial nanocellulose (BNC) membranes in an aqueous environment used as tissue reconstruction substrates for cerebral aneurysmal neck defects. Nano‐mechanical evaluation, performed using instrumented nano‐indentation, shows with very low normal loads between 0.01 to 0.5 mN, in the presence of deionized water. Mechanical testing and characterization reveals that the nano‐scale response of BNC behaves similar to blood vessel walls with a very low Young´s modulus, E (0.0025 to 0.04 GPa), and an evident creep effect (26.01 ± 3.85 nm s^?1). These results confirm a novel multi‐functional membrane using BNC and rendered magnetic with local adhesion of iron‐oxide magnetic nanoparticles.     

Reductive Amination Reaction for the Functionalization of Cellulose Nanocrystals

Cellulose nanocrystals (CNCs) represent intriguing biopolymeric nanocrystalline materials, that are biocompatible, sustainable and renewable, can be chemically functionalized and are endowed with exceptional mechanical properties. Recently, studies have been performed to prepare CNCs with extraordinary photophysical properties, also by means of their functionalization with organic light-emitting fluorophores. In this paper, we used the reductive amination reaction to chemically bind 4-(1-pyrenyl)butanamine selectively to the reducing termini of sulfated or neutral CNCs (S_CNC and N_CNC) obtained from sulfuric acid or hydrochloric acid hydrolysis. The functionalization reaction is simple and straightforward, and it induces the appearance of the typical pyrene emission profile in the functionalized materials. After a characterization of the new materials performed by ATR-FTIR and fluorescence spectroscopies, we demonstrate luminescence quenching of the decorated N_CNC by copper (II) sulfate, hypothesizing for these new functionalized materials an application in water purification technologies.     

Selective water‐permeable channels induced by polystyrene brushes within hairy nanocellulose/cellulose acetate membrane

Hairy nanocellulose (NC) was prepared by in‐situ admicellar polymerization of styrene on NC surface in the presence of cetyltrimethylammonium bromide through a stepwise fashion. It was also tried to achieve three hairy NCs with different polystyrene (PS) brush contents (i.e. 40, 50, and 80%) through altering monomer initial concentration. Then, NC and three hairy NCs were separately added into cellulose acetate (CA) solutions to fabricate membranes via the phase inversion technique. Transmission electron microscope images show that NC and three hairy NCs are spherical‐shaped nanoparticles. Results of Fourier transform infrared spectra provide clear evidence of PS brush being attached to the NC surfaces. Thermal gravimetric analysis confirms that increasing styrene initial concentration leads to enhanced PS content of hairy NCs. Results also elucidate that dispersions of prepared hairy NCs are highly stable even at high loading levels. It was found that incorporation of 1 wt% hairy NC with optimum brush content of 50% within CA membranes results in the increasing membrane water permeability from 7 to 40 l/m² hr with no change in its selectivity. Indeed, new interactions induced by PS brushes at hairy NC/CA interfaces result in the creation of connected channels at the interfaces which facilitate water transport through the membrane. This study provides insights into the key role that PS brushes play in overcoming the dispersion problems of NC in nonpolar media and offers guidelines to tailor channels within hairy NC/CA membrane for enhanced filtration performance. Copyright © 2017 John Wiley & Sons, Ltd.     

More Than Meets the Eye in Bacterial Cellulose: Biosynthesis,Bioprocessing, and Applications in Advanced Fiber Composites

Bacterial cellulose (BC) nanofibers are one of the stiffest organic materials produced by nature. It consists of pure cellulose without the impurities that are commonly found in plant‐based cellulose. This review discusses the metabolic pathways of cellulose‐producing bacteria and the genetic pathways of Acetobacter xylinum. The fermentative production of BC and the bioprocess parameters for the cultivation of bacteria are also discussed. The influence of the composition of the culture medium, pH, temperature, and oxygen content on the morphology and yield of BC are reviewed. In addition, the progress made to date on the genetic modification of bacteria to increase the yield of BC and the large‐scale production of BC using various bioreactors, namely static and agitated cultures, stirred tank, airlift, aerosol, rotary, and membrane reactors, is reviewed. The challenges in commercial scale production of BC are thoroughly discussed and the efficiency of various bioreactors is compared. In terms of the application of BC, particular emphasis is placed on the utilization of BC in advanced fiber composites to manufacture the next generation truly green, sustainable and renewable hierarchical composites.