Addition of Cellulose Nanofibers to Control Surface Roughness for Hydrophobic Ceramic Coatings.

Hydrophobic ceramic coatings are used for a variety of applications. Generally, hydrophobic coating surfaces are obtained by reducing the surface energy of the coating material or by forming a highly textured surface. Reducing the surface energy of the coating material requires additional costs and processing and changes the surface properties of the ceramic coating. In this study, we introduce a simple method to improve the hydrophobicity of ceramic coatings by implementing a textured surface without chemical modification of the surface. The ceramic coating solution was first prepared by adding cellulose nanofibers (CNFs) and then applied to a polypropylene (PP) substrate. The surface roughness increased as the amount of added CNFs increased, increasing the water contact angle of the surface. When the amount of CNFs added was corresponding to 10% of the solid content, the surface roughness average of the area was 43.8 µm. This is an increase of approximately 140% from 3.1 µm (the value of the surface roughness of the surface without added CNFs). In addition, the water contact angle of the coating with added CNF increased to 145.0°, which was 46% higher than that without the CNFs. The hydrophobicity of ceramic coatings with added CNFs was better because of changes in the surface topography. After coating and drying, the CNFs randomly accumulated inside the ceramic coating layer, forming a textured surface. Thus, hydrophobicity was improved by implementing a rugged ceramic surface without revealing the surface of the CNFs inside the ceramic layer.

Ferritin Nanocage Conjugated Hybrid Hydrogel for Tissue Engineering and Drug Delivery Applications.

Hydrogels have recently been attractive in various drug delivery and tissue engineering applications because of their structural similarities to the natural extracellular matrix. Despite enormous advances in the application of hydrogels, poor mechanical properties and lack of control for the release of drugs and biomolecules act as major barriers for widespread clinical applications. To overcome these challenges, we developed both physically and covalently conjugated nanocage-laden hydrogels between the surface of the nanocage and a gelatin methacryloyl (GelMA) hydrogel matrix. Ferritin and its empty-core equivalent apoferritin were used as nanocages that could be easily incorporated into a GelMA hydrogel via physical bonding. To fabricate covalently conjugated nanocage-laden GelMA hydrogels, ferritin and apoferritin were chemically modified to present the methacryloyl groups, ferritin methacryloyl (FerMA) and apoferritin methacryloyl (ApoMA), respectively. The covalently conjugated FerMA- and ApoMA-GelMA hydrogels offered a better ability to tune mechanical properties compared with those prepared by direct dispersion of ferritin and apoferritin into GelMA hydrogels with physical bonding, without affecting their porosity or cell growth. Furthermore, the ability of the nanocage to release small chemical compounds was confirmed by performing a cumulative release test on fluorescein isothiocyanate (FITC) encapsulated apoferritin and ApoMA incorporated GelMA hydrogels by pH stimulus. Thus, the nanocage incorporated hydrogels have emerged as excellent materials for drug delivery and tissue engineering applications.

Enhanced Interfacial Adhesion of Polydimethylsiloxane (PDMS) by Control of the Crosslink Density.

In this paper, we report a simple, fast, and one-step approach to improve the adhesion force of polydimethylsiloxane (PDMS) by incorporating inorganic nanoparticles that can control the physical, mechanical, and adhesion properties of the PDMS. An organic/inorganic PDMS-based composite was fabricated by the hydrosilylation of vinyl-decorated silica nanoparticles (v-SNPs) and the PDMS. The v-SNP/PDMS composite showed a significantly decreased elastic modulus and increased elongation compared with that of pristine SNPs incorporated with the PDMS composite (SNP/PDMS) and pristine PDMS. Furthermore, the v-SNP/PDMS composite exhibited a low glass-transition temperature and sharp crystallization and melting peaks in the differential scanning calorimetry curve compared with those of pristine PDMS and the SNP/PDMS composite. Moreover, the v-SNP/PDMS composite showed a high swelling ratio and crosslinked molecular weight and low gel fraction. These results may originate from the suppression of the PDMS-curing networks as the addition of the v-SNPs creates a low curing density because of the chemical bonding between PDMS and the v-SNPs. Finally, the v-SNP/PDMS composite showed an improvement of ~426% in the adhesion force compared with pristine PDMS and the SNP/PDMS composite. We anticipate that this v-SNP/PDMS composite could be used as a highly adhesive and hydrophobic coating material for various applications in industry.

Biocompatible Carbon Nanotube-Based Hybrid Microfiber for Implantable Electrochemical Actuator and Flexible Electronic Applications.

Biocompatible, electrically conductive microfibers with superior mechanical properties have received a great attention due to their potential applications in various biomedical applications such as implantable medical devices, biosensors, artificial muscles, and microactuators. Here, we developed an electrically conductive and mechanically stable carbon nanotube-based microactuator with a low degradability that makes it usable for an implantable device in the body or biological environments. The microfiber was composed of hyaluronic acid (HA) hydrogel and single-wall carbon nanotubes (SWCNTs) (HA/SWCNT). HA hydrogel acts as biosurfactant and ion-conducting binder to improve the dispersion of SWCNTs resulting in enhanced electrical and mechanical properties of the hybrid microfiber. In addition, HA was crosslinked to prevent the leaking of the nanotubes from the composite. Crosslinking of HA hydrogel significantly enhances Young's modulus, the failure strain, the toughness, the stability of the electrical conductivity, and the resistance to biodegradation and creep of hybrid microfibers. The obtained crosslinked HA/SWCNT hybrid microfibers show an excellent capacitance and actuation behavior under mechanical loading with a low potential of ±1 V in a biological environment. Furthermore, the HA/SWCNT microfibers exhibit an excellent in vitro viability. Finally, the biocompatibility is shown through the resolution of an early inflammatory response in less than 3 weeks after the implantation of the microfibers in the subcutaneous tissue of mice.

Flexible and Stretchable PEDOT-Embedded Hybrid Substrates for Bioengineering and Sensory Applications.

Herein, we introduce a flexible, biocompatible, robust and conductive electrospun fiber mat as a substrate for flexible and stretchable electronic devices for various biomedical applications. To impart the electrospun fiber mats with electrical conductivity, poly(3,4-ethylenedioxythiophene) (PEDOT), a conductive polymer, was interpenetrated into nitrile butadiene rubber (NBR) and poly(ethylene glycol) dimethacrylate (PEGDM) crosslinked electrospun fiber mats. The mats were fabricated with tunable fiber orientation, random and aligned, and displayed elastomeric mechanical properties and high conductivity. In addition, bending the mats caused a reversible change in their resistance. The cytotoxicity studies confirmed that the elastomeric and conductive electrospun fiber mats support cardiac cell growth, and thus are adaptable to a wide range of applications, including tissue engineering, implantable sensors and wearable bioelectronics.

Reversible Redox Activity by Ion-pH Dually Modulated Duplex Formation of i-Motif DNA with Complementary G-DNA.

The unique biological features of supramolecular DNA have led to an increasing interest in biomedical applications such as biosensors. We have developed an i-motif and G-rich DNA conjugated single-walled carbon nanotube hybrid materials, which shows reversible conformational switching upon external stimuli such as pH (5 and 8) and presence of ions (Li⁺ and K⁺). We observed reversible electrochemical redox activity upon external stimuli in a quick and robust manner. Given the ease and the robustness of this method, we believe that pH- and ion-driven reversible DNA structure transformations will be utilized for future applications for developing novel biosensors.

COF-Net on CNT-Net as a Molecularly Designed, Hierarchical Porous Chemical Trap for Polysulfides in Lithium-Sulfur Batteries.

The hierarchical porous structure has garnered considerable attention as a multiscale engineering strategy to bring unforeseen synergistic effects in a vast variety of functional materials. Here, we demonstrate a "microporous covalent organic framework (COF) net on mesoporous carbon nanotube (CNT) net" hybrid architecture as a new class of molecularly designed, hierarchical porous chemical trap for lithium polysulfides (Li2Sx) in Li-S batteries. As a proof of concept for the hybrid architecture, self-standing COF-net on CNT-net interlayers (called "NN interlayers") are fabricated through CNT-templated in situ COF synthesis and then inserted between sulfur cathodes and separators. Two COFs with different micropore sizes (COF-1 (0.7 nm) and COF-5 (2.7 nm)) are chosen as model systems. The effects of the pore size and (boron-mediated) chemical affinity of microporous COF nets on Li2Sx adsorption phenomena are theoretically investigated through density functional theory calculations. Benefiting from the chemical/structural uniqueness, the NN interlayers effectively capture Li2Sx without impairing their ion/electron conduction. Notably, the COF-1 NN interlayer, driven by the well-designed microporous structure, allows for the selective deposition/dissolution (i.e., facile solid-liquid conversion) of electrically inert Li2S. As a consequence, the COF-1 NN interlayer provides a significant improvement in the electrochemical performance of Li-S cells (capacity retention after 300 cycles (at charge/discharge rate = 2.0 C/2.0 C) = 84% versus 15% for a control cell with no interlayer) that lies far beyond those accessible with conventional Li-S technologies.

Heterolayered, one-dimensional nanobuilding block mat batteries.

The rapidly approaching smart/wearable energy era necessitates advanced rechargeable power sources with reliable electrochemical properties and versatile form factors. Here, as a unique and promising energy storage system to address this issue, we demonstrate a new class of heterolayered, one-dimensional (1D) nanobuilding block mat (h-nanomat) battery based on unitized separator/electrode assembly (SEA) architecture. The unitized SEAs consist of wood cellulose nanofibril (CNF) separator membranes and metallic current collector-/polymeric binder-free electrodes comprising solely single-walled carbon nanotube (SWNT)-netted electrode active materials (LiFePO4 (cathode) and Li4Ti5O12 (anode) powders are chosen as model systems to explore the proof of concept for h-nanomat batteries). The nanoporous CNF separator plays a critical role in securing the tightly interlocked electrode-separator interface. The SWNTs in the SEAs exhibit multifunctional roles as electron conductive additives, binders, current collectors and also non-Faradaic active materials. This structural/physicochemical uniqueness of the SEAs allows significant improvements in the mass loading of electrode active materials, electron transport pathways, electrolyte accessibility and misalignment-proof of separator/electrode interface. As a result, the h-nanomat batteries, which are easily fabricated by stacking anode SEA and cathode SEA, provide unprecedented advances in the electrochemical performance, shape flexibility and safety tolerance far beyond those achievable with conventional battery technologies. We anticipate that the h-nanomat batteries will open 1D nanobuilding block-driven new architectural design/opportunity for development of next-generation energy storage systems.

Graphene oxide and laponite composite films with high oxygen-barrier properties.

The design and fabrication of oxygen barrier films is important for both fundamental and industrial applications. We prepared three different thin films composed of graphene oxide (GO) and laponite (LN), a typical low cost inorganic clay, with the GO/LN volume ratios of 1.9/0.1, 1.7/0.3 and 1.5/0.5 together with a double layer film of the GO and LN. We found that the films with GO/LN = 1.9/0.1 and the double layers exhibited high oxygen barrier and oxygen transmission rate values that reached 0.55 and 0.37 cm(3) per m(2) per atm per day, respectively, which were much lower than those of the films prepared from the pure GO, only LN and GO/LN = 1.7/0.3 and 1.5/0.5. This study is important for the design and fabrication of a film from GO-based all inorganic nanomaterials for applications in gas-barrier membranes.

Multifunctional semi-interpenetrating polymer network-nanoencapsulated cathode materials for high-performance lithium-ion batteries.

As a promising power source to boost up advent of next-generation ubiquitous era, high-energy density lithium-ion batteries with reliable electrochemical properties are urgently requested. Development of the advanced lithium ion-batteries, however, is staggering with thorny problems of performance deterioration and safety failures. This formidable challenge is highly concerned with electrochemical/thermal instability at electrode material-liquid electrolyte interface, in addition to structural/chemical deficiency of major cell components. Herein, as a new concept of surface engineering to address the abovementioned interfacial issue, multifunctional conformal nanoencapsulating layer based on semi-interpenetrating polymer network (semi-IPN) is presented. This unusual semi-IPN nanoencapsulating layer is composed of thermally-cured polyimide (PI) and polyvinyl pyrrolidone (PVP) bearing Lewis basic site. Owing to the combined effects of morphological uniqueness and chemical functionality (scavenging hydrofluoric acid that poses as a critical threat to trigger unwanted side reactions), the PI/PVP semi-IPN nanoencapsulated-cathode materials enable significant improvement in electrochemical performance and thermal stability of lithium-ion batteries.

Direct electrospray deposition of graphene onto paper and effect of binder on its surface resistance.

The electrospray-deposited patterns of graphene onto filter paper were characterized to study the effect of cellulose acetate phthalate (CAP) binder on the surface resistance of the resulting paper. The amount of CAP determines the extent of penetration of graphene into the heterogeneous networks, because graphene gets anchored and crowded into the network with CAP. A graphene-dispersed ink was prepared in water using sodium dodecylbenzenesulfonate, and this ink was used to fabricate graphene-coated paper (GCP) by electrospray deposition technique. The SEM images of the GCP revealed the impregnation of graphene into the filter paper. The mechanical properties and surface resistance of the GCP were studied using a universal testing machine (UTM) and indigenous four-probe meter, respectively. The low-cost GCP prepared in this study showed relatively low surface resistance (96.2 omega/sq) owing to the effective electro-conducting pathway provided by the crowded and impregnated deposition of grapheme onto the filter paper. Consequently, CAP improved the electrical and mechanical characteristics of GCP, even though only a small amount of graphene was used during deposition.

Cellulosic binder-assisted formation of graphene-paper electrode with flat surface and porous internal structure.

We have reported the fabrication of flexible graphene-paper electrode (GPE) with a flat surface, whose internal structure has been formed with gradient porous build-up (from the surface to the 2-hydroxyethyl cellulose (HC)-coated paper). HC solution was used as a binder to form the gradient porous graphene layer, enabling it to create an anchoring force between the porous graphene layer and the filter paper. The morphology of GPE was investigated using a scanning electron microscope, and the surface resistance of the GPE as a function of graphene content was determined using four-probe method. The electrochemical performance of the GPE was evaluated using a three-electrode test cell by cyclic voltammetry. The gravimetric capacitance of GPE was found to be 120 F per gram of graphene, and the capacitance retention was within ca. 96% for over 500 cycles. This could be attributed to both the low surface resistance resulting from the flat surface and the high electrochemical activity caused by the gradient porous structure. This unique structure not only offers an enhanced conductivity and good electrical contact between the electrode and electrolyte but also helps GPE to maintain good cyclic stability, proving its potential for use in various rechargeable and portable energy-storage devices.

Tough supersoft sponge fibers with tunable stiffness from a DNA self-assembly technique.

Tough and soft: Highly porous, spongelike materials self-assemble by calcium ion condensation of DNA-wrapped carbon nanotubes (SWNTs-DNA; see picture, IL = ionic liquid). The toughness, modulus, and swellability of the electrically conductive sponges can be tuned by controlling the density and strength of interfiber junctions. The sponges have compliances similar to the softest natural tissue, while robust interfiber junctions give high toughness.

Switchable redox activity by proton fuelled DNA nano-machines.

The switching electrochemical property of an SWNT/DNA hybrid can be produced through reversible conformational changes between the closed and open state originating from the pH-responding i-motif DNA which significantly improves its molecular switching and stability by hydrophobic interactions with SWNTs.

The Peculiar Response of DNA Hydrogel Fibers to a Salt and pH Stimulus.

DNA hydrogels which are composed of an entangled network without a crosslinker are synthesized and examined in regards to their sensitivity to salt and pH changes. The DNA hydrogel fibers only exhibited a marked response - that is a fast and large change in length - under biological conditions ([Na(+) ] = 0.15 M at pH = 7) and are therefore suitable materials for bio-inspired devices.

Electrochemical pH oscillations of ethyl viologen/ionic liquid.

A reversible and robust electrochemical pH oscillator was achieved using an ethyl viologen/ionic liquid (IL) aqueous solution under an applied redox potential in a batch reactor, where the IL incorporated into the pH oscillator increased the stability of the pH oscillation by acting as an electron buffer solution.

Swelling behavior of chitosan hydrogels in ionic liquid-water binary systems.

The swelling behavior of chitosan hydrogels in ionic liquid-water binary systems was studied using hydrophilic room-temperature ionic liquids (RTILs) to elucidate the swelling mechanism of chitosan hydrogels. No penetration of RTIL into a dry chitosan material was observed. Swelling was achieved by soaking in water-RTIL binary mixtures, with larger swelling observed at higher water contents. In one instance, the binary mixture was acidic and produced larger than expected swelling due to the dissociation of the amine groups in the chitosan. The equilibrium binary system content behavior of the chitosan hydrogels depended upon the amount of free water, which is a measure of the number of water molecules that do not interact with the ionic liquid. After evaporation of water, remnant RTIL remained in the chitosan network and hardness testing indicated a plasticization effect, suggesting that the RTIL molecularly mixed with the chitosan. Chitosan hydrogels containing only RTIL were prepared by dropping pure RTIL onto a fully preswollen hydrogel followed by water evaporation. This method may be a useful means for preparing air-stable swollen chitosan gels.