Anisotropic,Transparent Films with Aligned Cellulose Nanofibers

Transparent films or substrates are ubiquitously used in photonics and optoelectronics, with glass and plastics as traditional choice of materials. Transparent films made of cellulose nanofibers are reported recently. However, all these films are isotropic in nature. This work, for the first time, reports a remarkably facile and effective approach to fabricating anisotropic transparent films directly from wood. The resulting films exhibit an array of exceptional optical and mechanical properties. The well‐aligned cellulose nanofibers in natural wood are maintained during delignification, leading to an anisotropic film with high transparency (≈90% transmittance) and huge intensity ratio of transmitted light up to 350%. The anisotropic film with well‐aligned cellulose nanofibers has a mechanical tensile strength of up to 350 MPa, nearly three times of that of a film with randomly distributed cellulose nanofibers. Atomistic mechanics modeling further reveals the dependence of the film mechanical properties on the alignment of cellulose nanofibers through the film thickness direction. This study also demonstrates guided liquid transport in a mesoporous, anisotropic wood film and its possible application in enabling new nanoelectronic devices. These unique and highly desirable properties of the anisotropic transparent film can potentially open up a range of green electronics and nanofluidics.     

From Wood to Textiles: Top‐Down Assembly of Aligned Cellulose Nanofibers

Advanced textiles made of macroscopic fibers are usually prepared from synthetic fibers, which have changed lives over the past century. The shortage of petrochemical resources, however, greatly limits the development of the textile industry. Here, a facile top‐down approach for fabricating macroscopic wood fibers for textile applications (wood‐textile fibers) comprising aligned cellulose nanofibers directly from natural wood via delignification and subsequent twisting is demonstrated. Inherently aligned cellulose nanofibers are well retained, while the microchannels in the delignified wood are squeezed and totally removed by twisting, resulting in a dense structure with approximately two times higher mechanical strength (106.5 vs 54.9 MPa) and ≈20 times higher toughness (7.70 vs 0.36 MJ m^?3) than natural wood. Dramatically different from natural wood, which is brittle in nature, the resultant wood‐textile fibers are highly flexible and bendable, likely due to the twisted structures. The wood‐textile fibers also exhibit excellent knitting properties and dyeability, which are critical for textile applications. Furthermore, functional wood‐textile fibers can be achieved by preinfiltrating functional materials in the delignified wood film before twisting. This top‐down approach of fabricating aligned macrofibers is simple, scalable, and cost‐effective, representing a promising direction for the development of smart textiles and wearable electronics.     

Large‐Scale Direct‐Writing of Aligned Nanofibers for Flexible Electronics

Nanofibers/nanowires usually exhibit exceptionally low flexural rigidities and remarkable tolerance against mechanical bending, showing superior advantages in flexible electronics applications. Electrospinning is regarded as a powerful process for this 1D nanostructure; however, it can only be able to produce chaotic fibers that are incompatible with the well‐patterned microstructures in flexible electronics. Electro‐hydrodynamic (EHD) direct‐writing technology enables large‐scale deposition of highly aligned nanofibers in an additive, noncontact, real‐time adjustment, and individual control manner on rigid or flexible, planar or curved substrates, making it rather attractive in the fabrication of flexible electronics. In this Review, the ground‐breaking research progress in the field of EHD direct‐writing technology is summarized, including a brief chronology of EHD direct‐writing techniques, basic principles and alignment strategies, and applications in flexible electronics. Finally, future prospects are suggested to advance flexible electronics based on orderly arranged EHD direct‐written fibers. This technology overcomes the limitations of the resolution of fabrication and viscosity of ink of conventional inkjet printing, and represents major advances in manufacturing of flexible electronics.     

High‐Performance Sodium‐Ion Battery Anode via Rapid Microwave Carbonization of Natural Cellulose Nanofibers with Graphene Initiator

Cellulose is a promising natural bio‐macromolecule due to its abundance, renewability and low cost. Here, a new method is developed to prepare pre‐sodiated carbonaceous anodes for sodium‐ion batteries (SIBs) from cellulose nanofibers (CNFs) under microwave irradiation for potential ultrafast and large‐scale manufacturing. While direct carbonization of CNFs through microwave treatment is usually impossible due to the weak microwave absorption of CNFs, it is found that a small amount of reduced graphene oxide (rGO) can act as an effective initiator. Microwaving rGO releases extremely high energy, giving rise to local ultrahigh temperature as well as ultrahigh heating rate, which then induces the fast carbonization of CNFs and the production of pre‐sodiated carbonaceous materials within seconds. The sodium in the carbonaceous materials, introduced from the carbonization of CNFs containing sodium‐ion carboxyl, offer favorable spaces for sodiation/desodiation, which improves the electrochemical performance of the sodium‐inserted carbonaceous anode. When the microwaved rGO‐CNF (MrGO‐CNF) is used as an anode for SIBs, a high initial capacity of 558 mAh g^?1 is delivered and the capacity of 340 mAh g^?1 remains after 200 cycles. The excellent reversible capacity and cycling stability indicate MrGO‐CNF a promising anode for sodium‐ion batteries.     

Toward High Strength and High Electrical Conductivity in Super‐Aligned Carbon Nanotubes Reinforced Copper

The miniaturization of electronic products is drawing higher demand in the strength and conductivity of conductors. This work demonstrates the possibility of substantially increasing the dislocation density in copper to enhance the strength of super‐aligned carbon nanotubes (SACNTs) reinforced copper matrix composites (SACNT/Cu) without compromising the electrical conductivity. High strain is introduced into pure copper and SACNT/Cu by accumulative roll‐bonding (ARB) process up to 16 cycles at ambient temperature. SACNTs with initial laminated distribution turn out to be dispersed uniformly with maintained directional arrangement inside the copper matrix after ARB, which can then effectively block the motion of dislocations. Therefore, large number of dislocations propagated by large strains can be accumulated without subdivision. The accumulated dislocations will result into strain hardening, which is the major strengthening mechanism in SACNT/Cu after ARB. Furthermore, the contribution of dislocations to resistivity increase is little, thus maintaining high electrical conductivity. As a result, a high tensile strength (505 MPa) combined with a high electrical conductivity (90% IACS) is achieved in large‐sized composite sheet.

     

Composites of Bacterial Cellulose and Small Molecule‐Decorated Gold Nanoparticles for Treating Gram‐Negative Bacteria‐Infected Wounds

Bacterial infections, especially multidrug‐resistant bacterial infections, are an increasingly serious problem in the field of wound healing. Herein, bacterial cellulose (BC) decorated by 4,6‐diamino‐2‐pyrimidinethiol (DAPT)‐modified gold nanoparticles (Au‐DAPT NPs) is presented as a dressing (BC‐Au‐DAPT nanocomposites) for treating bacterially infected wounds. BC‐Au‐DAPT nanocomposites have better efficacy (measured in terms of reduced minimum inhibition concentration) than most of the antibiotics (cefazolin/sulfamethoxazole) against Gram‐negative bacteria, while maintaining excellent physicochemical properties including water uptake capability, mechanical strain, and biocompatibility. On Escherichia coli‐ or Pseudomonas aeruginosa‐infected full‐thickness skin wounds on rats, the BC‐Au‐DAPT nanocomposites inhibit bacterial growth and promote wound repair. Thus, the BC‐Au‐DAPT nanocomposite system is a promising platform for treating superbug‐infected wounds.     

Super‐Resolution Nonlinear Photothermal Microscopy

Super‐resolution fluorescence microscopy enables imaging of fluorescent structures beyond the diffraction limit. However, this technique cannot be applied to weakly fluorescent cellular components or labels. As an alternative, photothermal microscopy based on nonradiative transformation of absorbed energy into heat has demonstrated imaging of nonfluorescent structures including single molecules and ~1‐nm gold nanoparticles. However, previously photothermal imaging has been performed with a diffraction‐limited resolution only. Herein, super‐resolution, far‐field photothermal microscopy based on nonlinear signal dependence on the laser energy is introduced. Among various nonlinear phenomena, including absorption saturation, multiphoton absorption, and signal temperature dependence, signal amplification by laser‐induced nanobubbles around overheated nano‐objects is explored. A Gaussian laser beam profile is used to demonstrate the image spatial sharpening for calibrated 260‐nm metal strips, resolving of a plasmonic nanoassembly, visualization of 10‐nm gold nanoparticles in graphene, and hemoglobin nanoclusters in live erythrocytes with resolution down to 50 nm. These nonlinear phenomena can be used for 3D imaging with improved lateral and axial resolution in most photothermal methods, including photoacoustic microscopy.     

N‐Doped Carbon Nanofibers with Interweaved Nanochannels for High‐Performance Sodium‐Ion Storage

Although graphite materials have been applied as commercial anodes in lithium‐ion batteries (LIBs), there still remain abundant spaces in the development of carbon‐based anode materials for sodium‐ion batteries (SIBs). Herein, an electrospinning route is reported to fabricate nitrogen‐doped carbon nanofibers with interweaved nanochannels (NCNFs‐IWNC) that contain robust interconnected 1D porous channels, produced by removal of a Te nanowire template that is coelectrospun within carbon nanofibers during the electrospinning process. The NCNFs‐IWNC features favorable properties, including a conductive 1D interconnected porous structure, a large specific surface area, expanded interlayer graphite‐like spacing, enriched N‐doped defects and active sites, toward rapid access and transport of electrolyte and electron/sodium ions. Systematic electrochemical studies indicate that the NCNFs‐IWNC exhibits an impressively high rate capability, delivering a capacity of 148 mA h g^?1 at current density of as high as 10 A g^?1, and has an attractively stable performance over 5000 cycles. The practical application of the as‐designed NCNFs‐IWNC for a full SIBs cell is further verified by coupling the NCNFs‐IWNC anode with a FeFe(CN)₆ cathode, which displays a desirable cycle performance, maintaining acapacity of 97 mA h g^?1 over 100 cycles.     

Electrospinning Nanofibers as Uniaxially Aligned Arrays and Layer‐by‐Layer Stacked Films

The conventional procedure for electrospinning has been modified to generate nanofibers as uniaxially aligned arrays over large areas. The key to the success of this method was the use of a collector composed of two conductive strips separated by an insulating gap of variable width. Directed by electrostatic interactions, the charged nanofibers were stretched to span across the gap and became uniaxially aligned arrays. Two types of gaps have been demonstrated: void gaps and gaps made of a highly insulating material. When a void gap was used, the nanofibers could readily be transferred onto the surfaces of other substrates for various applications. When an insulating substrate was involved, the electrodes could be patterned in various designs on the solid insulator. In both cases, the nanofibers could be conveniently stacked into multi‐layered architectures with controllable hierarchical structures. This new version of electrospinning has already been successfully applied to a range of different materials that include organic polymers, carbon, ceramics, and composites.     

Muscle‐Inspired Highly Anisotropic,Strong, Ion‐Conductive Hydrogels

Biological tissues generally exhibit excellent anisotropic mechanical properties owing to their well‐developed microstructures. Inspired by the aligned structure in muscles, a highly anisotropic, strong, and conductive wood hydrogel is developed by fully utilizing the high–tensile strength of natural wood, and the flexibility and high‐water content of hydrogels. The wood hydrogel exhibits a high–tensile strength of 36 MPa along the longitudinal direction due to the strong bonding and cross‐linking between the aligned cellulose nanofibers (CNFs) in wood and the polyacrylamide (PAM) polymer. The wood hydrogel is 5 times and 500 times stronger than the bacterial cellulose hydrogels (7.2 MPa) and the unmodified PAM hydrogel (0.072 MPa), respectively, representing one of the strongest hydrogels ever reported. Due to the negatively charged aligned CNF, the wood hydrogel is also an excellent nanofluidic conduit with an ionic conductivity of up to 5 × 10^?4 S cm^–1 at low concentrations for highly selective ion transport, akin to biological muscle tissue. The work offers a promising strategy to fabricate a wide variety of strong, anisotropic, flexible, and ionically conductive wood‐based hydrogels for potential biomaterials and nanofluidic applications.