Reversible flowering of CuO nanoclusters via conversion reaction for dual-ion Li metal batteries.

Dual-ion Li metal batteries based on non-flammable SO2-in-salt inorganic electrolytes ( Li-SO2 batteries) offer high safety and energy density. The use of cupric oxide (CuO) as a self-activating cathode material achieves a high specific capacity with cost-effective manufacturing in Li-SO2 batteries, but its cycle retention performance deteriorates owing to the significant morphological changes of the cathode active materials. Herein, we report the catalytic effect of carbonaceous materials used in the cathode material of Li-SO2 batteries, which act as templates to help recrystallize the active materials in the activation and conversion reactions. We found that the combination of oxidative-cyclized polyacrylonitrile (PAN) with N-doped carbonaceous materials and multi-yolk-shell CuO (MYS-CuO) nanoclusters as cathode active materials can significantly increase the specific capacity to 315.9 mAh g- 1 (93.8% of the theoretical value) at 0.2 C, which corresponds to an energy density of 1295 Wh kgCuO-1, with a capacity retention of 84.46% at the 200th cycle, and the cathode exhibited an atypical blossom-like morphological change.

Graphene collage on Ni-rich layered oxide cathodes for advanced lithium-ion batteries.

The energy storage performance of lithium-ion batteries (LIBs) depends on the electrode capacity and electrode/cell design parameters, which have previously been addressed separately, leading to a failure in practical implementation. Here, we show how conformal graphene (Gr) coating on Ni-rich oxides enables the fabrication of highly packed cathodes containing a high content of active material (~99 wt%) without conventional conducting agents. With 99 wt% LiNi0.8Co0.15Al0.05O2 (NCA) and electrode density of ~4.3 g cm-3, the Gr-coated NCA cathode delivers a high areal capacity, ~5.4 mAh cm-2 (~38% increase) and high volumetric capacity, ~863 mAh cm-3 (~34% increase) at a current rate of 0.2 C (~1.1 mA cm-2); this surpasses the bare electrode approaching a commercial level of electrode setting (96 wt% NCA; ~3.3 g cm-3). Our findings offer a combinatorial avenue for materials engineering and electrode design toward advanced LIB cathodes.

Graphene/PVDF Composites for Ni-rich Oxide Cathodes Toward High-Energy Density Li-ion Batteries.

Li-ion batteries (LIBs) employ porous, composite-type electrodes, where few weight percentages of carbonaceous conducting agents and polymeric binders are required to bestow electrodes with electrical conductivity and mechanical robustness. However, the use of such inactive materials has limited enhancements of battery performance in terms of energy density and safety. In this study, we introduced graphene/polyvinylidene fluoride (Gr/PVdF) composites in Ni-rich oxide cathodes for LIBs, replacing conventional conducting agents, carbon black (CB) nanoparticles. By using Gr/PVdF suspensions, we fabricated highly dense LiNi0.85Co0.15Al0.05O2 (NCA) cathodes having a uniform distribution of conductive Gr sheets without CB nanoparticles, which was confirmed by scanning spreading resistance microscopy mode using atomic force microscopy. At a high content of 99 wt.% NCA, good cycling stability was shown with significantly improved areal capacity (Qareal) and volumetric capacity (Qvol), relative to the CB/PVdF-containing NCA electrode with a commercial-level of electrode parameters. The NCA electrodes using 1 wt.% Gr/PVdF (0.9:0.1) delivered a high Qareal of ~3.7 mAh cm-2 (~19% increment) and a high Qvol of ~774 mAh cm-3 (~18% increment) at a current rate of 0.2 C, as compared to the conventional NCA electrode. Our results suggest a viable strategy for superseding conventional conducting agents (CB) and improving the electrochemical performance of Ni-rich cathodes for advanced LIBs.

Alkali-Metal-Mediated Reversible Chemical Hydrogen Storage Using Seawater.

The economic viability and systemic sustainability of a green hydrogen economy are primarily dependent on its storage. However, none of the current hydrogen storage methods meet all the targets set by the US Department of Energy (DoE) for mobile hydrogen storage. One of the most promising routes is through the chemical reaction of alkali metals with water; however, this method has not received much attention owing to its irreversible nature. Herein, we present a reconditioned seawater battery-assisted hydrogen storage system that can provide a solution to the irreversible nature of alkali-metal-based hydrogen storage. We show that this system can also be applied to relatively lighter alkali metals such as lithium as well as sodium, which increases the possibility of fulfilling the DoE target. Furthermore, we found that small (1.75 cm2) and scaled-up (70 cm2) systems showed high Faradaic efficiencies of over 94%, even in the presence of oxygen, which enhances their viability.

Seawater-Mediated Solar-to-Sodium Conversion by Bismuth Vanadate Photoanode- Photovoltaic Tandem Cell: Solar Rechargeable Seawater Battery.

Conversion of sunlight to chemical energy based on photoelectrochemical (PEC) processes has been considered as a promising strategy for solar energy harvesting. Here, we propose a novel platform that converts solar energy into sodium (Na) as a solid-state solar fuel via the PEC oxidation of natural seawater, for which a Na ion-selective ceramic membrane is employed together with photoelectrode (PE)-photovoltaic (PV) tandem cell. Using an elaborately modified bismuth vanadate-based PE in tandem with crystalline silicon PV, we demonstrate unassisted solar-to-Na conversion (equivalent to solar charge of seawater battery) with an unprecedentedly high efficiency of 8% (expected operating point under 1 sun) and measured operation efficiency of 5.7% (0.2 sun) and long-term stability, suggesting a new benchmark for low-cost, efficient, and scalable solid solar fuel production. The sodium turns easily into electricity on demand making the device a nature-friendly, monolithic solar rechargeable seawater battery.

Rechargeable Seawater Batteries-From Concept to Applications.

Harvesting energy from natural resources is of significant interest because of their abundance and sustainability. Seawater is the most abundant natural resource on earth, covering two-thirds of the surface. The rechargeable seawater battery is a new energy storage platform that enables interconversion of electrical energy and chemical energy by tapping into seawater as an infinite medium. Here, an overview of the research and development activities of seawater batteries toward practical applications is presented. Seawater batteries consist of anode and cathode compartments that are separated by a Na-ion conducting membrane, which allows only Na+ ion transport between the two electrodes. The roles and drawbacks of the three key components, as well as the development concept and operation principles of the batteries on the basis of previous reports are covered. Moreover, the prototype manufacturing lines for mass production and automation, and potential applications, particularly in marine environments are introduced. Highlighting the importance of engineering the cell components, as well as optimizing the system level for a particular application and thereby successful market entry, the key issues to be resolved are discussed, so that the seawater battery can emerge as a promising alternative to existing rechargeable batteries.

Analysis of Temporal Change in Voice Quality After Thyroidectomy: Single-institution Prospective Study.

OBJECTIVES: This study analyzed the temporal changes of voice quality after thyroidectomy and assessed the predictive perioperative parameters of postthyroidectomy voice disorder (PTVD). STUDY DESIGN: This is a prospective cohort study. METHODS: From March 2011 to July 2014, 559 patients who underwent thyroidectomy with or without central neck dissection were prospectively enrolled. All patients underwent prospective voice evaluation using the subjective and objective comprehensive battery of assessments, preoperatively and postoperatively at 1 week, 1 month, 3 months, 6 months, and 12 months. RESULTS: Fundamental frequency (F0) was not significantly decreased during the postoperative follow-up. Maximal vocal pitch (MVP) and maximal intensity were not recovered, even at 1 year postoperatively, whereas the Grade, Roughness, Breathiness, Asthenia, Strain scale reached preoperative value at postoperative 3-6 months and voice handicap index at 1 year. Postoperative 1-month MVP was the best predictor for PTVD, and the cut-off value was 80% of preoperative value. Wide surgical extent and high preoperative F0 were the parameters that significantly correlated with PTVD (P = 0.021 and P < 0.001, respectively), and large tumor, higher preoperative MVP, and lower postoperative 1-month F0 were significantly associated with permanent PTVD (P = 0.028, P < 0.001, and P = 0.003, respectively). CONCLUSIONS: Different recovery patterns of voice parameters should be considered in preoperative counseling. Intensive voice therapy may be needed for patients with the ability to produce higher pitch than normal preoperatively and wide surgical extent.

Predicting Extrathyroidal Extension in Patients With Papillary Thyroid Microcarcinoma According to a BRAF Mutation.

OBJECTIVES: The aim of this study was to evaluate the association between preoperative parameters and extrathyroidal extension (ETE) of papillary thyroid microcarcinoma (PTMC) according to the BRAF mutation and to evaluate the preoperative predictability of ETE. METHODS: We analyzed the medical records of 332 patients with PTMC (140 in the BRAF- group and 192 in the BRAF+ group). The presence of ETE was subjected to a correlation analysis with age, sex, tumor size, clinical nodal status, and ultrasonography (US) findings. Among the US findings, the correlation between tumors and the thyroid capsule was categorized into four groups; US group A, intraparechymal; US group B, tumor abutting the capsule <50% of diameter; US group C, tumor abutting >50% of diameter; and US group D, tumor destroyed the capsule. The predictive value of ETE, including sensitivity, specificity, and positive and negative predictive values were evaluated. RESULTS: Tumor size and US group were significantly correlated with gross ETE in the BRAF- and BRAF+ groups. Tumor size of 0.5 cm and US groups B and C in the BRAF- group were cutoff values for gross ETE, with a negative predictive value of 100%, whereas tumor size of 0.7 cm and US groups A and B in the BRAF+ group had negative predictive values of 92.4% and 100%, respectively. CONCLUSION: Excluding of ETE by US was categorized according to tumor size and US findings. A different categorization to exclude ETE is needed according to the BRAF mutation.

A Metal-Organic Framework Derived Porous Cobalt Manganese Oxide Bifunctional Electrocatalyst for Hybrid Na-Air/Seawater Batteries.

Spinel-structured transition metal oxides are promising non-precious-metal electrocatalysts for oxygen electrocatalysis in rechargeable metal-air batteries. We applied porous cobalt manganese oxide (CMO) nanocubes as the cathode electrocatalyst in rechargeable seawater batteries, which are a hybrid-type Na-air battery with an open-structured cathode and a seawater catholyte. The porous CMO nanocubes were synthesized by the pyrolysis of a Prussian blue analogue, Mn3[Co(CN)6]2·nH2O, during air-annealing, which generated numerous pores between the final spinel-type CMO nanoparticles. The porous CMO electrocatalyst improved the redox reactions, such as the oxygen evolution/reduction reactions, at the cathode in the seawater batteries. The battery that used CMO displayed a voltage gap of ∼0.53 V, relatively small compared to that of the batteries employing commercial Pt/C (∼0.64 V) and Ir/C (∼0.73 V) nanoparticles and without any catalyst (∼1.05 V) at the initial cycle. This improved performance was due to the large surface area (catalytically active sites) and the high oxidation states of the randomly distributed Co and Mn cations in the CMO. Using a hard carbon anode, the Na-metal-free seawater battery exhibited a good cycle performance with an average discharge voltage of ∼2.7 V and a discharge capacity of ∼190 mAh g-1hard carbon during 100 cycles (energy efficiencies of 74-79%).

Effect of Tianeptine on Depressed Tinnitus Patients.

BACKGROUND AND OBJECTIVES: Tianeptine is a tricyclic antidepressant that has a novel pharmacological property: it increases the reuptake of 5-hydroxytryptamine. Recent studies have reported that the prevalence of depression is greater in patients with tinnitus than in control subjects who do not have tinnitus. The purpose of this study was to assess the efficacy of tianeptine for the relief of tinnitus, especially in patients with depressive mood. SUBJECTS AND METHODS: Among a total of 52 tinnitus patients, 15 had depressive mood. The depressed tinnitus patients were prescribed Stablon® 12.5 mg once daily for 1 month without any other drug. We assessed the severity of tinnitus, level of depression, and the quality of sleep in these patients by using the Tinnitus Handicap Inventory (THI), Beck Depression Inventory (BDI), and Pittsburgh Sleep Quality Index (PSQI). Hearing impairment and severity of tinnitus were measured with pure tone audiometry, speech audiometry, and tinnitograms. These evaluations were conducted before and after medication treatment. RESULTS: For the 15 depressed tinnitus patients, THI scores significantly correlated with BDI and PSQI scores prior to medication treatment. These results showed that the discomfort of tinnitus was closely related to depression and sleep disorder. After medication treatment, THI and BDI scores significantly decreased, indicating that tinnitus and depression improved. However, no significant alteration in PSQI score was observed, indicating that there was no improvement in sleep quality. CONCLUSIONS: In the treatment of depressed tinnitus patients, tianeptine might be an efficient drug to treat both tinnitus and depression. However, tianeptine is unlikely to improve the quality of sleep in these patients.

Hydrothermally Grown In-doped ZnO Nanorods on p-GaN Films for Color-tunable Heterojunction Light-emitting-diodes.

The incorporation of doping elements in ZnO nanostructures plays an important role in adjusting the optical and electrical properties in optoelectronic devices. In the present study, we fabricated 1-D ZnO nanorods (NRs) doped with different In contents (0% ~ 5%) on p-GaN films using a facile hydrothermal method, and investigated the effect of the In doping on the morphology and electronic structure of the NRs and the electrical and optical performances of the n-ZnO NRs/p-GaN heterojunction light emitting diodes (LEDs). As the In content increased, the size (diameter and length) of the NRs increased, and the electrical performance of the LEDs improved. From the electroluminescence (EL) spectra, it was found that the broad green-yellow-orange emission band significantly increased with increasing In content due to the increased defect states (oxygen vacancies) in the ZnO NRs, and consequently, the superposition of the emission bands centered at 415 nm and 570 nm led to the generation of white-light. These results suggest that In doping is an effective way to tailor the morphology and the optical, electronic, and electrical properties of ZnO NRs, as well as the EL emission property of heterojunction LEDs.

Electrospun manganese-cobalt oxide hollow nanofibres synthesized via combustion reactions and their lithium storage performance.

Mesoporous hollow fibres of MnCo2O4 and CoMn2O4 were synthesized by electrospinning and highly exothermic oxygen-mediated combustion reactions during calcination, in which the heating rate affected the final fibre morphology (e.g., single- or double-shell). The anodes consisting of hollow fibres showed excellent electrochemical properties for lithium-ion batteries.

Surface-Tunable Bioluminescence Resonance Energy Transfer via Geometry-Controlled ZnO Nanorod Coordination.

The use of ZnO nanorods (NRs) as an effective coordinator and biosensing platform to create bioluminescence resonance energy transfer (BRET) is reported. Herein, a hydrothermal approach is applied to obtain morphologically controlled ZnO NRs, which are directly bound to luciferase (Luc) and carboxy-modified quantum dot (QD) acting as a donor-acceptor pair for BRET. BRET efficiency varies significantly with the geometry of ZnO NRs, which modulates the coordination between hexahistidine-tagged Luc (Luc-His6 ) and QD, owing to the combined effect of the total surface area consisting of (001) and (100) planes and their surface polarities. Unlike typical QD-BRET reactions with metal ions (e.g., zinc ions), a geometry-controlled ZnO NR platform can facilitate the design of surface-initiated BRET sensors without being supplemented by copious metal ions: the geometry-controlled ZnO NR platform can therefore pave the way for nanostructure-based biosensors with enhanced analytical performance.

One-dimensional manganese-cobalt oxide nanofibres as bi-functional cathode catalysts for rechargeable metal-air batteries.

Rechargeable metal-air batteries are considered a promising energy storage solution owing to their high theoretical energy density. The major obstacles to realising this technology include the slow kinetics of oxygen reduction and evolution on the cathode (air electrode) upon battery discharging and charging, respectively. Here, we report non-precious metal oxide catalysts based on spinel-type manganese-cobalt oxide nanofibres fabricated by an electrospinning technique. The spinel oxide nanofibres exhibit high catalytic activity towards both oxygen reduction and evolution in an alkaline electrolyte. When incorporated as cathode catalysts in Zn-air batteries, the fibrous spinel oxides considerably reduce the discharge-charge voltage gaps (improve the round-trip efficiency) in comparison to the catalyst-free cathode. Moreover, the nanofibre catalysts remain stable over the course of repeated discharge-charge cycling; however, carbon corrosion in the catalyst/carbon composite cathode degrades the cycling performance of the batteries.

Scalable integration of Li5FeO4 towards robust, high-performance lithium-ion hybrid capacitors.

Lithium-ion hybrid capacitors have attracted great interest due to their high specific energy relative to conventional electrical double-layer capacitors. Nevertheless, the safety issue still remains a drawback for lithium-ion capacitors in practical operational environments because of the use of metallic lithium. Herein, single-phase Li5FeO4 with an antifluorite structure that acts as an alternative lithium source (instead of metallic lithium) is employed and its potential use for lithium-ion capacitors is verified. Abundant Li(+) amounts can be extracted from Li5FeO4 incorporated in the positive electrode and efficiently doped into the negative electrode during the first electrochemical charging. After the first Li(+) extraction, Li(+) does not return to the Li5FeO4 host structure and is steadily involved in the electrochemical reactions of the negative electrode during subsequent cycling. Various electrochemical and structural analyses support its superior characteristics for use as a promising lithium source. This versatile approach can yield a sufficient Li(+)-doping efficiency of >90% and improved safety as a result of the removal of metallic lithium from the cell.

Chronic rhinosinusitis with nasal polyps and without nasal polyps is associated with increased expression of lysophosphatidic acid-related molecules.

BACKGROUND: Chronic sinusitis with nasal polyps (CRSwNPs) or CRS without NPs (CRSsNPs) is associated with expression of various cytokines. Lysophosphatidic acid (LPA) generated by autotaxin (ATX), LPA-producing enzyme, initiates signaling cascade involved in the inflammatory responses and participates in diverse biological processes through LPA receptors, including cytokine production. We analyzed the expression and distribution patterns of LPA-related molecules in nasal secretion and sinus mucosa of normal controls and patients with CRSwNPs and CRSsNPs, to evaluate the possible effects of the ATX-LPA receptor axis on the pathogenesis of CRS. METHODS: LPA levels in nasal secretion and the expression and distribution patterns of ATX and LPA receptors 1-3 (LPA1-3) in sinus mucosa were investigated using ELISA, real-time polymerase chain reaction, Western blot, and immunohistochemistry. We elucidated the effect of CRS-relevant cytokines on the expression of ATX and LPA receptors, using cultured sinus epithelial cells, and investigated the effect of LPA on the expression of CRS-relevant cytokines, using sinus mucosa explant culture. RESULTS: LPA, ATX, and LPA1-3 levels are increased in CRSwNPs and CRSsNPs. ATX and LPA1-3 were localized to superficial epithelium, submucosal glands in normal and inflammatory mucosa, but in inflammatory mucosa, they were found in inflammatory cells. LPA1-3 were noted in endothelium. Sinus mucosa explant stimulated with LPA increasingly produced IL-4, IL-5, interferon gamma, and TNF-alpha, and in cultured epithelial cells stimulated with CRS-relevant cytokines, ATX, and LPA1-3 were differentially induced. CONCLUSION: LPA in human sinus mucosa may play important roles in the pathogenesis of CRS, contributing to produce CRS-related cytokines. LPA-related molecules were increased in CRS, which may attribute to CRS-related cytokines.

Expression of 11ß-hydroxysteroid dehydrogenase 1 and 2 in patients with chronic rhinosinusitis and their possible contribution to local glucocorticoid activation in sinus mucosa.

BACKGROUND: It has been suggested that glucocorticoids might act in target tissues to increase their own intracellular availability in response to inflammatory stimuli. These mechanisms depend on the local metabolism of glucocorticoids catalyzed by 11ß-hydroxysteroid dehydrogenase 1 (11ß-HSD1) and 11ß-hydroxysteroid dehydrogenase 2 (11ß-HSD2). OBJECTIVE: This study is to investigate the effect of chronic rhinosinusitis (CRS) on expression of 11ß-HSD1, 11ß-HSD2, steroidogenic enzymes (cytochrome P450, family 11, subfamily B, polypeptide 1 [CYP11B1] and cytochrome P450, family 11, subfamily A, polypeptide 1 [CYP11A1]), and endogenous cortisol levels in human sinus mucosa. Expression levels were compared with those of healthy control subjects. METHODS: The expression levels of 11ß-HSD1, 11ß-HSD2, CYP11B1, CYP11A1, and cortisol were measured in healthy control subjects, patients with CRS with nasal polyps, and patients with CRS without nasal polyps by using real-time PCR, Western blotting, immunohistochemistry, and ELISA. Expression levels of 11ß-HSD1, 11ß-HSD2, CYP11B1, CYP11A1, and cortisol were determined in cultured epithelial cells treated with CRS-relevant cytokines. The conversion ratio of cortisone to cortisol was evaluated by using the small interfering RNA technique, 11ß-HSD1 inhibitor, and measurement of 11ß-HSD1 activity. RESULTS: 11ß-HSD1, CYP11B1, and cortisol levels increased in patients with CRS with nasal polyps and those with CRS without nasal polyps, but 11ß-HSD2 expression decreased. In cultured epithelial cells treated with IL-4, IL-5, IL-13, IL-1ß, TNF-α, and TGF-ß1, 11ß-HSD1 expression and activity increased in parallel with expression levels of CYP11B1 and cortisol, but the production of 11ß-HSD2 decreased. The small interfering RNA technique or the measurement of 11ß-HSD1 activity showed that the sinus epithelium activates cortisone to cortisol in an 11ß-HSD-dependent manner. CONCLUSION: These results indicate that CRS-relevant cytokines can modulate the expression of 11ß-HSD1, 11ß-HSD2, and CYP11B1 in the sinus mucosa, resulting in increasing intracellular concentrations of bioactive glucocorticoids.

Generalized self-assembly of scalable two-dimensional transition metal oxide nanosheets.

Two-dimensional (2D) transition metal oxide systems present exotic electronic properties and high specific surface areas, and also demonstrate promising applications ranging from electronics to energy storage. Yet, in contrast to other types of nanostructures, the question as to whether we could assemble 2D nanomaterials with an atomic thickness from molecules in a general way, which may give them some interesting properties such as those of graphene, still remains unresolved. Herein, we report a generalized and fundamental approach to molecular self-assembly synthesis of ultrathin 2D nanosheets of transition metal oxides by rationally employing lamellar reverse micelles. It is worth emphasizing that the synthesized crystallized ultrathin transition metal oxide nanosheets possess confined thickness, high specific surface area and chemically reactive facets, so that they could have promising applications in nanostructured electronics, photonics, sensors, and energy conversion and storage devices.

Zr4+ doping in Li4Ti5O12 anode for lithium-ion batteries: open Li+ diffusion paths through structural imperfection.

One-dimensional nanomaterials have short Li(+) diffusion paths and promising structural stability, which results in a long cycle life during Li(+) insertion and extraction processes in lithium rechargeable batteries. In this study, we fabricated one-dimensional spinel Li4Ti5O12 (LTO) nanofibers using an electrospinning technique and studied the Zr(4+) doping effect on the lattice, electronic structure, and resultant electrochemical properties of Li-ion batteries (LIBs). Accommodating a small fraction of Zr(4+) ions in the Ti(4+) sites of the LTO structure gave rise to enhanced LIB performance, which was due to structural distortion through an increase in the average lattice constant and thereby enlarged Li(+) diffusion paths rather than changes to the electronic structure. Insulating ZrO2 nanoparticles present between the LTO grains due to the low Zr(4+) solubility had a negative effect on the Li(+) extraction capacity, however. These results could provide key design elements for LTO anodes based on atomic level insights that can pave the way to an optimal protocol to achieve particular functionalities.

Synthesis of mesoporous TiO2/SiO2 hybrid films as an efficient photocatalyst by polymeric micelle assembly.

Thermally stable mesoporous TiO2/SiO2 hybrid films with pore size of 50 nm have been synthesized by adopting the polymeric micelle-assembly method. A triblock copolymer, poly(styrene-b-2-vinyl pyridine-b-ethylene oxide), which serves as a template for the mesopores, was utilized to form polymeric micelles. The effective interaction of titanium tetraisopropoxide (TTIP) and tetraethyl orthosilicate (TEOS) with the polymeric micelles enabled us to fabricate stable mesoporous films. By changing the molar ratio of TEOS and TTIP, several mesoporous TiO2/SiO2 hybrid films with different compositions can be synthesized. The presence of amorphous SiO2 phase effectively retards the growth of anatase TiO2 crystal in the pore walls and retains the original mesoporous structure, even at higher temperature (650 °C). These TiO2/SiO2 hybrid films are of very high quality, without any cracks or voids. The addition of SiO2 phase to mesoporous TiO2 films not only adsorbs more organic dyes, but also significantly enhances the photocatalytic activity compared to mesoporous pure TiO2 film without SiO2 phase.