Synthesis and Electrochemical Characterization of Nitrate-Doped Polypyrrole/Ag Nanowire Nanorods as Supercapacitors.

Polypyrrole (PPy)-capped silver nanowire (Ag NW) nanomaterials (core-shell rod-shaped Ag NW@PPy) were synthesized using a one-port suspension polymerization technique. The thickness of the PPy layer on the 50 nm thickness/15 µm length Ag NW was effectively controlled to 10, 40, 50, and 60 nm. Thin films cast from one-dimensional conductive Ag NW@PPy formed a three-dimensional (3D) conductive porous network structure and provided excellent electrochemical performance. The 3D Ag NW@PPy network can significantly reduce the internal resistance of the electrode and maintain structural stability. As a result, a high specific capacitance of 625 F/g at a scan rate of 1 mV/s was obtained from the 3D porous Ag NW@PPy composite film. The cycling performance over a long period exceeding 10,000 cycles was also evaluated. We expect that our core-shell-structured Ag NW@PPy composites and their 3D porous structure network films can be applied as electrochemical materials for the design and manufacturing of supercapacitors and other energy storage devices.

Promoting Homogeneous Zinc-Ion Transfer Through Preferential Ion Coordination Effect in Gel Electrolyte for Stable Zinc Metal Batteries.

Aqueous zinc metal batteries (AZMBs) are emerging energy storage systems that are poised to replace conventional lithium-ion batteries owing to their intrinsic safety, facile manufacturing process, economic benefits, and superior ionic conductivity. However, the issues of inferior anode reversibility and dendritic plating during operation remain challenging for the practical use of AZMBs. Herein, a gel electrolyte based on zwitterionic poly(sulfobetaine methacrylate) (poly(SBMA)) dissolved with different concentrations of ZnSO4 is proposed. Two-dimensional correlation spectroscopy based on Raman analysis reveals an enhanced interaction priority between the polar groups in SBMA and the dissolved ions as electrolyte concentration increases, which establishes a robust interaction and renders homogeneous ion distribution. Attributable to the modified coordination, zwitterionic gel polymer electrolyte with 5 mol kg-1 of ZnSO4 (ZGPE-5) facilitates stable zinc deposition and improves anode reversibility. By taking advantage of preferential coordination, a symmetrical cell evaluation employing ZGPE-5 demonstrates a cycle life over 3600 h, where ZGPE-5 also exerts a beneficial effect on the full cell cycling when assembled with Zn0.25 V2 O5 cathode. This study elucidates changes in the internal ion behavior that are dependent on electrolyte concentrations and pave the way for durable AZMBs.

Electroconductive, Adhesive, Non-Swelling, and Viscoelastic Hydrogels for Bioelectronics.

As a new class of materials, implantable flexible electrical conductors have recently been developed and applied to bioelectronics. An ideal electrical conductor requires high conductivity, tissue-like mechanical properties, low toxicity, reliable adhesion to biological tissues, and the ability to maintain its shape in wet physiological environments. Despite significant advances, electrical conductors that satisfy all these requirements are insufficient. Herein, a facile method for manufacturing a new conductive hydrogels through the simultaneous exfoliation of graphite and polymerization of zwitterionic monomers triggered by microwave irradiation is introduced. The mechanical properties of the obtained conductive hydrogel are similar to those of living tissue, which is ideal as a bionic adhesive for minimizing contact damage due to mechanical mismatches between hard electronics and soft tissues. Furthermore, it exhibits excellent adhesion performance, electrical conductivity, non-swelling, and high conformability in water. Excellent biocompatibility of the hydrogel is confirmed through a cytotoxicity test using C2C12 cells, a biocompatibility test on rat tissues, and their histological analysis. The hydrogel is then implanted into the sciatic nerve of a rat and neuromodulation is demonstrated through low-current electrical stimulation. This hydrogel demonstrates a tissue-like extraneuronal electrode, which possesses high conformability to improve the tissue-electronics interfaces, promising next-generation bioelectronics applications.

Advances in Colloidal Building Blocks: Toward Patchy Colloidal Clusters.

The scalable synthetic route to colloidal atoms has significantly advanced over the past two decades. Recently, colloidal clusters with DNA-coated cores called "patchy colloidal clusters" have been developed, providing a directional bonding with specific angle of rotation due to the shape complementarity between colloidal clusters. Through a DNA-mediated interlocking process, they are directly assembled into low-coordination colloidal structures, such as cubic diamond lattices. Herein, the significant progress in recent years in the synthesis of patchy colloidal clusters and their assembly in experiments and simulations is reviewed. Furthermore, an outlook is given on the emerging approaches to the patchy colloidal clusters and their potential applications in photonic crystals, metamaterials, topological photonic insulators, and separation membranes.

Lumbar Interbody Fusion and Osteobiologics for Lumbar Fusion.

Lumbar interbody fusion (LIF) is an excellent treatment option for a number of lumbar diseases. LIF can be performed through posterior, transforaminal, anterior, and lateral or oblique approaches. Each technique has its own pearls and pitfalls. Through LIF, segmental stabilization, neural decompression, and deformity correction can be achieved. Minimally invasive surgery has recently gained popularity and each LIF procedure can be performed using minimally invasive techniques to reduce surgery-related complications and improve early postoperative recovery. Despite advances in surgical technology, surgery-related complications after LIF, such as pseudoarthrosis, have not yet been overcome. Although autogenous iliac crest bone graft is the gold standard for spinal fusion, other bone substitutes are available to enhance fusion rate and reduce complications associated with bone harvest. This article reviews the surgical procedures and characteristics of each LIF and the osteobiologics utilized in LIF based on the available evidence.

AtELP4 a subunit of the Elongator complex in Arabidopsis, mediates cell proliferation and dorsoventral polarity during leaf morphogenesis.

The Elongator complex in eukaryotes has conserved tRNA modification functions and contributes to various physiological processes such as transcriptional control, DNA replication and repair, and chromatin accessibility. ARABIDOPSIS ELONGATOR PROTEIN 4 (AtELP4) is one of the six subunits (AtELP1-AtELP6) in Arabidopsis Elongator. In addition, there is an Elongator-associated protein, DEFORMED ROOTS AND LEAVES 1 (DRL1), whose homolog in yeast (Kti12) binds tRNAs. In this study, we explored the functions of AtELP4 in plant-specific aspects such as leaf morphogenesis and evolutionarily conserved ones between yeast and Arabidopsis. ELP4 comparison between yeast and Arabidopsis revealed that plant ELP4 possesses not only a highly conserved P-loop ATPase domain but also unknown plant-specific motifs. ELP4 function is partially conserved between Arabidopsis and yeast in the growth sensitivity toward caffeine and elevated cultivation temperature. Either single Atelp4 or drl1-102 mutants and double Atelp4 drl1-102 mutants exhibited a reduction in cell proliferation and changed the adaxial-abaxial polarity of leaves. In addition, the single Atelp4 and double Atelp4 drl1-102 mutants showed remarkable downward curling at the whole part of leaf blades in contrast to wild-type leaf blades. Furthermore, our genetic study revealed that AtELP4 might epistatically act on DRL1 in the regulation of cell proliferation and dorsoventral polarity in leaves. Taken together, we suggest that AtELP4 as part of the plant Elongator complex may act upstream of a regulatory pathway for adaxial-abaxial polarity and cell proliferation during leaf development.

Mucus-inspired organogel as an efficient absorbent and retention agent for volatile organic compounds.

Nasal mucus plays a key role in the sense of smell by absorbing and transporting chemicals to olfactory receptors. Inspired by the physical properties of mucus that enable it to transport molecules despite its high viscosity, we developed a polymeric organogel with similar viscosity and analyzed its general performance. Through qualitative and quantitative analysis, we confirmed that the matrix viscosity mainly affects the absorption and retention of volatile organic compounds (VOCs) and not their diffusion inside the matrix. Additionally, the vapor pressure of VOCs influences the absorption and retention efficiencies of the matrix. Finally, a detailed understanding of the properties of mucus along with the use of sol-gel transition enabled us to create an efficient VOC absorbent and retention agent.

Liquid-to-Solid Phase Transitions of Imidazolium-Based Zwitterionic Polymers Induced by Hofmeister Anions.

In this study, we compared the responses of two different types of zwitterionic polymers (ZPs), polyvinylimidzole sulfobetaine (poly(SBVI)) and polymethacrylate sulfobetaine (poly(SBMA)) to Hofmeister anions. Although the anions of the two ZPs were the same as the sulfonate anions and only the types of their cations were different from each other, the aggregation behavior of each in the salt aqueous solution was remarkably different. Consequently, poly(SBVI) exhibited both salting-in and salting-out effects depending on the type and concentration of salt, while poly(SBMA) only exhibited the anti-polyelectrolyte effect. The results of this study provide a deeper understanding of the behavior of zwitterionic polymers in salt solutions and will greatly expand their applications.

Fast and Large Shrinking of Thermoresponsive Hydrogels with Phase-Separated Structures.

Thermoresponsive poly(N-isopropylacrylamide) (PNIPAAm) hydrogels have been attracting attention in a variety of functional materials, such as biomaterials, because they exhibit a volume phase transition phenomenon near physiological temperatures. However, the slow kinetics and small volume shrinkage of bulk PNIPAAm hydrogels upon heating greatly limit their practical application. Here, we report PNIPAAm hydrogels with phase-separated structures that exhibited ultrafast shrinking upon heating. The phase separation into a PNIPAAm-rich phase and a water-rich phase was formed through aqueous polymerization in the presence of NaClO4 salt. Through structural analysis of the hydrogels, a topologically heterogeneous and porous structure was observed, which was highly dependent on the NaClO4 concentration in the polymerization step. Compared to conventional PNIPAAm hydrogels, the phase-separated hydrogels exhibited much faster and larger shrinkage upon heating. Simultaneously, the hydrogels quickly released a large amount of water owing to the effective water channels inside them. The present method can be widely applied to general hydrogels, and it can address the numerous limitations of hydrogels in terms of operating programmability and deformation efficiency.

Nanocomposite hydrogel actuators hybridized with various dimensional nanomaterials for stimuli responsiveness enhancement.

Hydrogel actuators, that convert external energy, such as pH, light, heat, magnetic field, and ion strength, into mechanical motion, have been utilized in sensors, artificial muscles, and soft robotics. For a practicality of the hydrogel actuators in a wide range of fields, an establishment of robust mechanical properties and rapid response are required. Several solutions have been proposed, for example, setting porous and anisotropy structures to hydrogels with nanocomposite materials to improve the response speed and deformation efficiency. In this review paper, we focused on hydrogel actuators including various nanocomposite by categorizing the dimensional aspects of additive materials. Moreover, we described the role of diverse additive materials in terms of the improvement of mechanical property and deformation efficiency of the hydrogel actuators. We assumed that this review will provide a beneficial guidance for strategies of developing nanocomposite hydrogel actuators and outlooks for the future research directions.

An Anisotropic Hydrogel Actuator Enabling Earthworm-Like Directed Peristaltic Crawling.

Peristaltic crawling, which is the moving mechanism of earthworm-like limbless creatures in narrow spaces, is a challenging target to mimic by using soft materials. Here we report an unprecedented hydrogel actuator that enables not only a peristaltic crawling motion but also reversing its direction. Our cylindrically processed hydrogel contains gold nanoparticles for photothermal conversion, a thermoresponsive polymer network for switching the electrical permittivity of the gel interior, and cofacially oriented 2D electrolytes (titanate nanosheets; TiNSs) to synchronously change their anisotropic electrostatic repulsion. When a hydrogel, which was designed to include cofacially oriented TiNSs along the cylindrical gel axis, is pointwisely photoirradiated with a visible-light laser, it spatiotemporally expands immediately (<0.5 s) and largely (80 % of its original length) in an isovolumetric manner. When the irradiation spot is moved along the cylindrical gel axis, the hydrogel undergoes peristaltic crawling due to quick and sequential elongation/contraction events and moves oppositely toward the laser scanning direction. Thus, when the scanning direction is switched, the crawling direction is reversed. When gold nanorods are used in place of gold nanoparticles, the hydrogel becomes responsive to a near-infrared light, which can deeply penetrate into bio tissues.

Thermoresponsive Surface-Grafted Gels: Controlling the Bulk Volume Change Properties by Surface-Localized Polymer Grafting with Various Densities.

We prepared poly(N-isopropylacrylamide-r-N-3-(aminopropyl)methacrylamide) (poly(NIPAAm-r-NAPMAm)) gels with poly NIPAAm (PNIPAAm) grafted only in the surface region (so-called thermoresponsive surface-grafted gels) with various graft densities and investigated the effect of the graft density on the bulk volume change properties, shrinking and swelling, in response to temperature changes. Initiators for atom-transfer radical polymerization (ATRP) and structurally analogous compounds were introduced at certain ratios onto the surface regions of the gels, and a subsequent activator regeneration by electron transfer ATRP of NIPAAm was conducted in aqueous media. The graft densities and molecular weights of the grafted polymers were evaluated from the increment in the dry mass of the gels and the amount of introduced ATRP initiators, which was measured by elemental analyses. Three-dimensional measuring laser microscopy revealed that the prepared gels had graft-density-dependent fine wrinkle structures on their surfaces. The surface-grafted gels induced the formation of skin layers during the shrinking process in response to a temperature increase, and their permeability strongly depended on the graft density. The graft density also controlled the kinetics of the swelling behavior in response to a temperature decrease. These physical properties were discussed on the basis of Young's modulus of the surface determined by an atomic force microscopy force curve measurement and the homogeneity of the surface polymer network observed by cryo-scanning electron microscopy. This makes it possible to arbitrarily control the characteristics of gels as open or semiclosed systems, which was uniquely determined by the designs of the surface gel networks.

Photonic water dynamically responsive to external stimuli.

Fluids that contain ordered nanostructures with periodic distances in the visible-wavelength range, anomalously exhibit structural colours that can be rapidly modulated by external stimuli. Indeed, some fish can dynamically change colour by modulating the periodic distance of crystalline guanine sheets cofacially oriented in their fluid cytoplasm. Here we report that a dilute aqueous colloidal dispersion of negatively charged titanate nanosheets exhibits structural colours. In this 'photonic water', the nanosheets spontaneously adopt a cofacial geometry with an ultralong periodic distance of up to 675 nm due to a strong electrostatic repulsion. Consequently, the photonic water can even reflect near-infrared light up to 1,750 nm. The structural colour becomes more vivid in a magnetic flux that induces monodomain structural ordering of the colloidal dispersion. The reflective colour of the photonic water can be modulated over the entire visible region in response to appropriate physical or chemical stimuli.

Thermoresponsive actuation enabled by permittivity switching in an electrostatically anisotropic hydrogel.

Electrostatic repulsion, long used for attenuating surface friction, is not typically employed for the design of bulk structural materials. We recently developed a hydrogel with a layered structure consisting of cofacially oriented electrolyte nanosheets. Because this unusual geometry imparts a large anisotropic electrostatic repulsion to the hydrogel interior, the hydrogel resisted compression orthogonal to the sheets but readily deformed along parallel shear. Building on this concept, here we show a hydrogel actuator that operates by modulating its anisotropic electrostatics in response to changes of electrostatic permittivity associated with a lower critical solution temperature transition. In the absence of substantial water uptake and release, the distance between the nanosheets rapidly expands and contracts on heating and cooling, respectively, so that the hydrogel lengthens and shortens significantly, even in air. An L-shaped hydrogel with an oblique nanosheet configuration can thus act as a unidirectionally proceeding actuator that operates without the need for external physical biases.

Thin and long silver nanowires self-assembled in ionic liquids as a soft template: electrical and optical properties.

Thin and long silver nanowires were successfully synthesized using the polyvinylpyrrolidone (PVP)-assisted polyol method in the presence of ionic liquids, tetrapropylammonium chloride and tetrapropylammonium bromide, which served as soft template salts. The first step involved the formation of Ag nanoparticles with a diameter of 40 to 50 nm through the reduction of silver nitrate. At the growing stage, the Ag nanoparticles were converted into thin and long one-dimensional wires, with uniform diameters of 30 ± 3 nm and lengths of up to 50 µm. These Ag nanowires showed an electrical conductivity of 0.3 × 10(5) S/cm, while the sheet resistance of a two-dimensional percolating Ag nanowire network exhibited a value of 20 Ω/sq with an optical transmittance of 93% and a low haze value.

Insight into the origin of the positive effects of imidazolium salt on electrocatalytic activity: ionic carbon nanotubes as metal-free electrocatalysts for oxygen reduction reaction.

We report remarkable metal-free electrocatalytic activities of the imidazolium salt-functionalized ionic multi-walled carbon nanotubes (IM-f-MWCNTs) in the oxygen reduction reaction (ORR). The electrocatalytic activity can be attributed to the induced polarization of the π-electrons of CNTs, thus accelerating interfacial electron transfer. The zwitterionic MWCNTs functionalized with poly(vinylimidazolium sulfonate) have a more positive surface charge and exhibit a better electrocatalytic activity than the poly(vinylbutylimidazolium chloride)-functionalized MWCNTs. The IM-f-MWCNTs showed better fuel selectivity than the commercial Pt/C electrocatalyst.

High-density assembly of gold nanoparticles with zwitterionic carbon nanotubes and their electrocatalytic activity in oxygen reduction reaction.

Gold nanoparticles (AuNPs) were assembled with high density onto multi-walled carbon nanotubes, which were functionalized with zwitterionic poly(imidazoliumsulfonate). The AuNP/zwitterionic CNT hybrids exhibited decent electrocatalytic activity in oxygen reduction reaction as the AuNP-based catalysts.

Electrocatalytic activity of nanoporous Pd and Pt: effect of structural features.

The electrocatalytic activities of nanoporous palladium (npPd) and platinum (npPt) for oxygen reduction reaction (ORR) under alkaline conditions and hydrogen peroxide electrochemical reactions under neutral conditions were examined. npPd and npPt were prepared by the electrochemical deposition of each metal from the corresponding metal precursor in the presence of reverse micelles of Triton X-100, directing highly porous microstructures. The nanoporous catalysts showed excellent electrocatalytic activity for both the ORR and hydrogen peroxide electrochemical oxidation/reduction due to the increased active surface area. In particular, the npPd exhibited superior ORR activity (i.e., more positive onset and half-wave potentials, higher current density and greater number of electrons transferred) despite the smaller roughness factor than the npPt and commercial Pt. The catalytic activity for the hydrogen peroxide electrochemical reactions was also higher while using npPd (i.e., faster electrode reaction kinetics, increased current densities, etc.) compared to npPt. The higher catalytic activity of npPd than that of npPt suggests an advantage of the unique npPd structure, composed of nano- as well as micro-porosity, in facilitating mass transport through the porous metal layer. The npPd exhibited amperometric current responses, induced by the oxidation as well as reduction of hydrogen peroxide, linearly proportional to the hydrogen peroxide concentration with a rapid response time (<~2 s), high sensitivity, and low detection limit (<1.8 µM).

A 12-year-old chronic form textiloma after revision surgery for infected spinal instrumentation.

Retained surgical gauze and the surrounding foreign body reaction constitute a mass referred to as a textiloma. Textiloma has acute and chronic forms; the acute form is symptomatic in the early postoperative period and the chronic form may be asymptomatic or display mild and nonspecific symptoms. Usually, textiloma after previously infected surgery has acute forms. We report here on a case of a 46-year-old male who had retained surgical gauze for 12 years. The patient had received revision surgery for infected spinal instrumentation 12-years previously and had no specific symptom after surgery. One month prior to the present admission, the patient experienced low back pain and left thigh pain. Based on the prior operative history and present imaging results, the patient was diagnosed with an abscess due to a foreign body reaction. The patient underwent surgery, which discovered retained gauze with granuloma. This case is the third longest reported case after entire spinal surgery and the longest time of textiloma after previously infected spine surgery.

Impact of anions on electrocatalytic activity in palladium nanoparticles supported on ionic liquid-carbon nanotube hybrids for the oxygen reduction reaction.

A series of palladium nanoparticles supported on carbon nanotubes (CNTs), which were functionalized covalently with imidazolium polymer salts with different anions, Pd/polyIL(X)-CNTs (IL=ionic liquid; X=Cl, Br, I, ClO(4), BF(4), PF(6)), were prepared to investigate the influence of imidazolim salt anions on electrocatalytic activity in the oxygen reduction reaction (ORR). The anions of the imidazolium moiety significantly impacted on the ORR kinetics in a 0.1 M solution of HClO(4). The electronically active surface area results are in good agreement with the order of the ORR kinetic activity of the supported Pd/polyIL(X)-CNTs (X: Cl>ClO(4)>BF(4)>Br≈PF(6)≫I). In contrast, owing to the facile anion exchange of halide anions with hydroxide anions, anion-dependent catalytic activity has not been observed in 0.1 M NaOH. Iterative ORR experiments in acid-base solutions demonstrated anion exchange on the electrode. These results indicate that subtly varied structures of the IL moiety profoundly influence the performance of IL-CNT hybrid materials and molecular-level control of interfacial interactions between the support material, catalysts, and electrolytes is important in the design of supported metal nanoparticle catalysts for fuel cells.