MoS2 Passivated Multilayer Graphene Membranes for Li-Ion Extraction From Seawater.

Abundant Li resources in the ocean are promising alternatives to refining ore, whose supplies are limited by the total amount and geopolitical imbalance of reserves in Earth's crust. Despite advances in Li+ extraction using porous membranes, they require screening other cations on a large scale due to the lack in precise control of pore size and inborn defects. Herein, MoS2 nanoflakes on a multilayer graphene membrane (MFs-on-MGM) that possess ion channels comprising i) van der Waals interlayer gaps for optimal Li+ extraction and ii) negatively charged vertical inlets for cation attraction, are reported. Ion transport measurements across the membrane reveal ≈6- and 13-fold higher selectivity for Li+ compared to Na+ and Mg2+ , respectively. Furthermore, continuous, stable Li+ extraction from seawater is demonstrated by integrating the membrane into a H2 and Cl2 evolution system, enabling more than 104 -fold decrease in the Na+ concentration and near-complete elimination of other cations.

Direct nanofluidic channels via hardening and wrinkling of thin polymer films.

In this study, we propose a rational route to create wrinkling patterns with individually controllable location and direction in thin polymer films. Optical and atomic force microscopy analysis confirmed the formation of straight wrinkles with a typical width of 1.51 to 1.55 µm and a height of 60 to 65 nm. Confocal fluorescence microscopy revealed that each wrinkle produces a continuous hollow channel that interconnects neighboring holes in the polymer film, demonstrating potential applications as nanoscale fluidic channel and reactor. Moreover, we propose a mechanism that considers the elastic deformation energy and interface energies as crucial parameters that govern the mechanical instabilities, which provides scaling relationships between the height, width, and thickness of the wrinkles. This offers additional opportunities for control over the size and aspect ratio of the wrinkles and channels.

Direct Observation of Carboxymethyl Cellulose and Styrene-Butadiene Rubber Binder Distribution in Practical Graphite Anodes for Li-Ion Batteries.

Despite the important role of carboxymethyl cellulose (CMC) and styrene-butadiene rubber (SBR) binders in graphite electrodes for Li-ion batteries, the direct analysis of these binders remains challenging, particularly at very low concentrations as in practical graphite anodes. In this paper, we report the systematic investigation of the physiochemical behavior of the CMC and SBR binders and direct observations of their distributions in practical graphite electrodes. The key to this unprecedented capability is combining the advantages of several analytic techniques, including laser-ablation laser-induced break-down spectroscopy, time of flight secondary ion mass spectrometry, and a surface and interfacial cutting analysis system. By correlating the vertical distribution with the adsorption behaviors of the CMC, our study reveals that the CMC migration toward the surface during the drying process depends on the degree of cross-linked binder-graphite network generation, which is determined by the surface property of graphite and CMC materials. The suggested analytical techniques enable the independent tracing of CMC and SBR, disclosing the different vertical distribution of SBR from that of the CMC binder in our practical graphite anodes. This achievement provides additional opportunity to analyze the correlation between the binder distribution and mechanical properties of the electrodes.

Electrical Double Layer of Supported Atomically Thin Materials.

The electrical double layer (EDL), consisting of two parallel layers of opposite charges, is foundational to many interfacial phenomena and unique in atomically thin materials. An important but unanswered question is how the "transparency" of atomically thin materials to their substrates influences the formation of the EDL. Here, we report that the EDL of graphene is directly affected by the surface energy of the underlying substrates. Cyclic voltammetry and electrochemical impedance spectroscopy measurements demonstrate that graphene on hydrophobic substrates exhibits an anomalously low EDL capacitance, much lower than what was previously measured for highly oriented pyrolytic graphite, suggesting disturbance of the EDL ("disordered EDL") formation due to the substrate-induced hydrophobicity to graphene. Similarly, electrostatic gating using EDL of graphene field-effect transistors shows much lower transconductance levels or even no gating for graphene on hydrophobic substrates, further supporting our hypothesis. Molecular dynamics simulations show that the EDL structure of graphene on a hydrophobic substrate is disordered, caused by the disruption of water dipole assemblies. Our study advances understanding of EDL in atomically thin limit.

Self-Powered Chemical Sensing Driven by Graphene-Based Photovoltaic Heterojunctions with Chemically Tunable Built-In Potentials.

Ultralow power chemical sensing is essential toward realizing the Internet of Things. However, electrically driven sensors must consume power to generate an electrical readout. Here, a different class of self-powered chemical sensing platform based on unconventional photovoltaic heterojunctions consisting of a top graphene (Gr) layer in contact with underlying photoactive semiconductors including bulk silicon and layered transition metal dichalcogenides is proposed. Owing to the chemically tunable electrochemical potential of Gr, the built-in potential at the junction is effectively modulated by absorbed gas molecules in a predictable manner depending on their redox characteristics. Such ability distinctive from bulk photovoltaic counterparts enables photovoltaic-driven chemical sensing without electric power consumption. Furthermore, it is demonstrated that the hydrogen (H2 ) sensing properties are independent of the light intensity, but sensitive to the gas concentration down to the 1 ppm level at room temperature. These results present an innovative strategy to realize extremely energy-efficient sensors, providing an important advancement for future ubiquitous sensing.

Annual Fluctuation in Chigger Mite Populations and Orientia Tsutsugamushi Infections in Scrub Typhus Endemic Regions of South Korea.

OBJECTIVES: Chigger mites are vectors for scrub typhus. This study evaluated the annual fluctuations in chigger mite populations and Orientia tsutsugamushi infections in South Korea. METHODS: During 2006 and 2007, chigger mites were collected monthly from wild rodents in 4 scrub typhus endemic regions of South Korea. The chigger mites were classified based on morphological characteristics, and analyzed using nested PCR for the detection of Orientia tsutsugamushi. RESULTS: During the surveillance period, the overall trapping rate for wild rodents was 10.8%. In total, 17,457 chigger mites (representing 5 genera and 15 species) were collected, and the average chigger index (representing the number of chigger mites per rodent), was 31.7. The monthly chigger index was consistently high (> 30) in Spring (March to April) and Autumn (October to November). The mite species included Leptotrombidium pallidum (43.5%), L. orientale (18.9%), L. scutellare (18.1%), L. palpale (10.6%), and L. zetum (3.6%). L. scutellare and L. palpale populations, were relatively higher in Autumn. Monthly O. tsutsugamushi infection rates in wild rodents (average: 4.8%) and chigger mites (average: 0.7%) peaked in Spring and Autumn. CONCLUSION: The findings demonstrated a bimodal pattern of the incidence of O. tsutsugamushi infections. Higher infection rates were observed in both wild rodents and chigger mites, in Spring and Autumn. However, this did not reflect the unimodal incidence of scrub typhus in Autumn. Further studies are needed to identify factors, such as human behavior and harvesting in Autumn that may explain this discordance.

Anomalous Photovoltaic Response of Graphene-on-GaN Schottky Photodiodes.

Graphene has attracted great attention as an alternative to conventional metallic or transparent conducting electrodes. Despite its similarities with conventional electrodes, recent studies have shown that a single-atom layer of graphene possesses unique characteristics, such as a tunable work function and transparencies for electric potential, reactivity, and wetting. Nevertheless, a systematic analysis of graphene and semiconductor junction characteristics has not yet been carried out. Here, we report the photoresponse characteristics of graphene-on-GaN Schottky junction photodiodes (Gr-GaN SJPDs), showing a typical rectifying behavior and distinct photovoltaic and photoelectric responses. Following the initial abrupt response to UV illumination, the Gr-GaN SJPDs exhibited a distinct difference in photocarrier dynamics depending on the applied bias voltage, which is characterized by either a negative or positive change in photocurrent with time. We propose underlying mechanisms for the anomalous photocarrier dynamics based on the interplay between electrostatic molecular interactions over the one-atom-thick graphene and GaN junction and trapped photocarriers at the defect states in the GaN thin film.

3D calcite heterostructures for dynamic and deformable mineralized matrices.

Scales are rooted in soft tissues, and are regenerated by specialized cells. The realization of dynamic synthetic analogues with inorganic materials has been a significant challenge, because the abiological regeneration sites that could yield deterministic growth behavior are hard to form. Here we overcome this fundamental hurdle by constructing a mutable and deformable array of three-dimensional calcite heterostructures that are partially locked in silicone. Individual calcite crystals exhibit asymmetrical dumbbell shapes and are prepared by a parallel tectonic approach under ambient conditions. The silicone matrix immobilizes the epitaxial nucleation sites through self-templated cavities, which enables symmetry breaking in reaction dynamics and scalable manipulation of the mineral ensembles. With this platform, we devise several mineral-enabled dynamic surfaces and interfaces. For example, we show that the induced growth of minerals yields localized inorganic adhesion for biological tissue and reversible focal encapsulation for sensitive components in flexible electronics.Minerals are rarely explored as building blocks for dynamic inorganic materials. Here, the authors derive inspiration from fish scales to create mutable surfaces based on arrays of calcite crystals, in which one end of each crystal is immobilized in and regenerated from silicone, and the other functional end is left exposed.

Enhanced piezoresponse of highly aligned electrospun poly(vinylidene fluoride) nanofibers.

Well-ordered nanostructure arrays with controlled densities can potentially improve material properties; however, their fabrication typically involves the use of complicated processing techniques. In this work, we demonstrate a uniaxial alignment procedure for fabricating poly(vinylidene fluoride) (PVDF) electrospun nanofibers (NFs) by introducing collectors with additional steps. The mechanism of the observed NF alignment, which occurs due to the concentration of lateral electric field lines around collector steps, has been elucidated via finite-difference time-domain simulations. The membranes composed of well-aligned PVDF NFs are characterized by a higher content of the PVDF ß-phase, as compared to those manufactured from randomly orientated fibers. The piezoelectric energy harvester, which was fabricated by transferring well-aligned PVDF NFs onto flexible substrates with Ag electrodes attached to both sides, exhibited a 2-fold increase in the output voltage and a 3-fold increase in the output current as compared to the corresponding values obtained for the device manufactured from randomly oriented NFs. The enhanced piezoresponse observed for the aligned PVDF NFs is due to their higher ß-phase content, denser structure, smaller effective radius of curvature during bending, greater applied strain, and higher fraction of contributing NFs.

Defect-Mediated Molecular Interaction and Charge Transfer in Graphene Mesh-Glucose Sensors.

We report the role of defects in enzymatic graphene field-effect transistor sensors by introducing engineered defects in graphene channels. Compared with conventional graphene sensors (Gr sensors), graphene mesh sensors (GM sensors), with an array of circular holes, initially exhibited a higher irreversible response to glucose, involving strong chemisorption to edge defects. However, after immobilization of glucose oxidase, the irreversibility of the responses was substantially diminished, without any reduction in the sensitivity of the GM sensors (i.e., -0.53 mV/mM for the GM sensor vs -0.37 mV/mM for Gr sensor). Furthermore, multiple cycle operation led to rapid sensing and improved the reversibility of GM sensors. In addition, control tests with sensors containing a linker showed that sensitivity was increased in Gr sensors but decreased in GM sensors. Our findings indicate that edge defects can be used to replace linkers for immobilization of glucose oxidase and improve charge transfer across glucose oxidase-graphene interfaces.

Switching of Photonic Crystal Lasers by Graphene.

Unique features of graphene have motivated the development of graphene-integrated photonic devices. In particular, the electrical tunability of graphene loss enables high-speed modulation of light and tuning of cavity resonances in graphene-integrated waveguides and cavities. However, efficient control of light emission such as lasing, using graphene, remains a challenge. In this work, we demonstrate on/off switching of single- and double-cavity photonic crystal lasers by electrical gating of a monolayer graphene sheet on top of photonic crystal cavities. The optical loss of graphene was controlled by varying the gate voltage Vg, with the ion gel atop the graphene sheet. First, the fundamental properties of graphene were investigated through the transmittance measurement and numerical simulations. Next, optically pumped lasing was demonstrated for a graphene-integrated single photonic crystal cavity at Vg below -0.6 V, exhibiting a low lasing threshold of ∼480 µW, whereas lasing was not observed at Vg above -0.6 V owing to the intrinsic optical loss of graphene. Changing quality factor of the graphene-integrated photonic crystal cavity enables or disables the lasing operation. Moreover, in the double-cavity photonic crystal lasers with graphene, switching of individual cavities with separate graphene sheets was achieved, and these two lasing actions were controlled independently despite the close distance of ∼2.2 µm between adjacent cavities. We believe that our simple and practical approach for switching in graphene-integrated active photonic devices will pave the way toward designing high-contrast and ultracompact photonic integrated circuits.

Observation of Charge Separation and Space-Charge Region in Single-Crystal P3HT/C60 Heterojunction Nanowires.

We directly observed charge separation and a space-charge region in an organic single-crystal p-n heterojunction nanowire, by means of scanning photocurrent microscopy. The axial p-n heterojunction nanowire had a well-defined planar junction, consisted of P3HT (p-type) and C60 (n-type) single crystals and was fabricated by means of the recently developed inkjet-assisted nanotransfer printing technique. The depletion region formed at the p-n junction was directly observed by exploring the spatial distribution of photogenerated carriers along the heterojunction nanowire under various applied bias voltages. Our study provides a facile approach toward the precise characterization of charge transport in organic heterojunction systems as well as the design of efficient nanoscale organic optoelectronic devices.

First Isolation of Severe Fever with Thrombocytopenia Syndrome Virus from Haemaphysalis longicornis Ticks Collected in Severe Fever with Thrombocytopenia Syndrome Outbreak Areas in the Republic of Korea.

Severe fever with thrombocytopenia syndrome (SFTS) is an emerging tick-borne infectious disease that is endemic to China, Japan, and the Republic of Korea (ROK). In this study, 8313 ticks collected from SFTS outbreak areas in the ROK in 2013 were used to detect the SFTS virus (SFTSV). A single SFTSV was isolated in cell culture from one pool of Haemaphysalis longicornis ticks collected from Samcheok-si, Gangwon Province, in the ROK. Phylogenetic analysis showed that the SFTSV isolate was clustered with the SFTSV strain from Japan, which was isolated from humans. To the best of our knowledge, this is the first isolation in the world of SFTSV in ticks collected from vegetation.

Reversible and Irreversible Responses of Defect-Engineered Graphene-Based Electrolyte-Gated pH Sensors.

We have studied the role of defects in electrolyte-gated graphene mesh (GM) field-effect transistors (FETs) by introducing engineered edge defects in graphene (Gr) channels. Compared with Gr-FETs, GM-FETs were characterized as having large increments of Dirac point shift (∼30-100 mV/pH) that even sometimes exceeded the Nernst limit (59 mV/pH) by means of electrostatic gating of H(+) ions. This feature was attributed to the defect-mediated chemisorptions of H(+) ions to the graphene edge, as supported by Raman measurements and observed cycling characteristics of the GM FETs. Although the H(+) ion binding to the defects increased the device response to pH change, this binding was found to be irreversible. However, the irreversible component showed relatively fast decay, almost disappearing after 5 cycles of exposure to solutions of decreasing pH value from 8.25 to 6.55. Similar behavior could be found in the Gr-FET, but the irreversible component of the response was much smaller. Finally, after complete passivation of the defects, both Gr-FETs and GM-FETs exhibited only reversible response to pH change, with similar magnitude in the range of 6-8 mV/pH.

Chemical and biological sensors based on defect-engineered graphene mesh field-effect transistors.

Graphene has been intensively studied for applications to high-performance sensors, but the sensing characteristics of graphene devices have varied from case to case, and the sensing mechanism has not been satisfactorily determined thus far. In this review, we describe recent progress in engineering of the defects in graphene grown by a silica-assisted chemical vapor deposition technique and elucidate the effect of the defects upon the electrical response of graphene sensors. This review provides guidelines for engineering and/or passivating defects to improve sensor performance and reliability.

Graphene as an Interfacial Layer for Improving Cycling Performance of Si Nanowires in Lithium-Ion Batteries.

Managing interfacial instability is crucial for enhancing cyclability in lithium-ion batteries (LIBs), yet little attention has been devoted to this issue until recently. Here, we introduce graphene as an interfacial layer between the current collector and the anode composed of Si nanowires (SiNWs) to improve the cycling capability of LIBs. The atomically thin graphene lessened the stress accumulated by volumetric mismatch and inhibited interfacial reactions that would accelerate the fatigue of Si anodes. By simply incorporating graphene at the interface, we demonstrated significantly enhanced cycling stability for SiNW-based LIB anodes, with retentions of more than 2400 mAh/g specific charge capacity over 200 cycles, 2.7 times that of SiNWs on a bare current collector.

The corrected QT (QTc) prolongation in hyperthyroidism and the association of thyroid hormone with the QTc interval.

PURPOSE: Ventricular repolarization is assessed using the QT interval corrected by the heart rate (QTc) via an electrocardiogram (ECG). Prolonged QTc is associated with an increased risk of arrhythmias and cardiac mortality. As there have been few reports regarding the effects of hyperthyroidism on ventricular repolarization, we studied the association between serum free thyroxine (free T4 [fT4]) and thyroid stimulating hormone (TSH) levels and the QTc interval. METHODS: Thirty-eight patients with hyperthyroidism (<30 years old) were included, and we used their clinical records and available ECGs (between August 2003 and August 2011) to evaluate the association between their fT4 and TSH levels and their QTc interval. In addition, we studied the ECGs of 72 age-matched patients with no hyperthyroidism (control group) and compared their data with that from the patients group. RESULTS: The QTc duration in patients with hyperthyroidism was significantly prolonged compared to that in the control subjects (P<0.001). In addition, the number of hyperthyroid patients with abnormal prolonged QTc was significantly higher than that in the control group (P<0.001). Among the patients with hyperthyroidism, patients with prolonged QTc and borderline QTc had higher fT4 levels and there was positive correlation between their fT4 levels and their QTc interval (P<0.05). However, no correlation was observed between their TSH levels and their QTc interval. CONCLUSION: We report that hyperthyroidism is associated with QTc prolongation. The correlation between the fT4 levels and the QTc interval suggests that thyroid status is associated with QTc values and the risk of cardiac mortality.

Time-dependent mechanical-electrical coupled behavior in single crystal ZnO nanorods.

Nanoscale time-dependent mechanical-electrical coupled behavior of single crystal ZnO nanorods was systematically explored, which is essential for accessing the long-term reliability of the ZnO nanorod-based flexible devices. A series of compression creep tests combined with in-situ electrical measurement was performed on vertically-grown single crystal ZnO nanorods. Continuous measurement of the current (I)-voltage (V) curves before, during, after the creep tests revealed that I is non-negligibly increased as a result of the time-dependent deformation. Analysis of the I-V curves based on the thermionic emission-diffusion theory allowed extraction of nanorod resistance, which was shown to decrease as time-dependent deformation. Finally, based on the observations in this study, a simple analytical model for predicting the reduction in nanorod resistance as a function of creep strain that is induced from diffusional mechanisms is proposed, and this model was demonstrated to be in an excellent agreement with the experimental results.

Strong interactive growth behaviours in solution-phase synthesis of three-dimensional metal oxide nanostructures.

Wet-chemical synthesis is a promising alternative to the conventional vapour-phase method owing to its advantages in commercial-scale production at low cost. Studies on nanocrystallization in solution have suggested that growth rate is commonly affected by the size and density of surrounding crystals. However, systematic investigation on the mutual interaction among neighbouring crystals is still lacking. Here we report on strong interactive growth behaviours observed during anisotropic growth of zinc oxide hexagonal nanorods arrays. In particular, we found multiple growth regimes demonstrating that the diameter of the rod is dependent on its height. Local interactions among the growing rods result in cases where height is irrelevant to the diameter, increased with increasing diameter or inversely proportional to the diameter. These phenomena originate from material diffusion and the size-dependent Gibbs-Thomson effect that are universally applicable to a variety of material systems, thereby providing bottom-up strategies for diverse three-dimensional nanofabrication.