Extending the Operational Lifetime of Electrochemiluminescence Devices by Installing a Floating Bipolar Electrode.

Electrochemiluminescence (ECL) holds significant promise for the development of cost-effective light-emitting devices because of its simple structure. However, conventional ECL devices (ECLDs) have a major limitation of short operational lifetimes, rendering them impractical for real-world applications. Typically, the luminescence of these devices lasts no longer than a few minutes during operation. In the current study, a novel architecture is provided for ECLDs that addresses this luminescence lifespan issue. The device architecture features an ECL active layer between two coplanar driving electrodes and a third floating bipolar electrode. The inclusion of the floating bipolar electrode enables modulating the electrical-field distribution within the active layer when a bias is applied between the driving electrodes. This, in turn, enables the use of opaque yet electrochemically stable noble metals as the driving electrodes while allowing ECL light to escape through the transparent floating bipolar electrode. A significant extension on operational lifetime is achieved, defined as the time required for the initial luminance (>100 cd m-2) to decrease by 50%, surpassing 1 h. This starkly contrasts the short lifetime (<1 min) attained by ECLDs in a conventional sandwich-type architecture with two transparent electrodes. These results provide simple strategies for developing durable ECL-based light-emitting devices.

An automated laser fluorination technique for high-precision analysis of three oxygen isotopes in silicates.

RATIONALE: The three oxygen isotopes in terrestrial/extraterrestrial silicates can provide geochemical and cosmochemical information about their origin and secondary processes that result from isotopic exchange. A laser fluorination technique has been widely used to extract oxygen from silicates for δ17 O and δ18 O measurements by isotope ratio mass spectrometry. Continued improvement of the techniques is still important for high-precision measurement of oxygen-isotopic ratios. METHODS: We adopted an automated lasing technique to obtain reproducible fluorination of silicates using a CO2 laser-BrF5 fluorination system connected online to an isotope ratio mass spectrometer. The automated lasing technique enables us to perform high-precision analysis of the three oxygen isotopes of typical reference materials (e.g., UWG2 garnet, NBS28 quartz and San Carlos olivine) and in-house references (mid-ocean ridge basalt glass and obsidian). The technique uses a built-in application of laser control with which the laser power can be varied in a programmed manner with a defocused beam which is in a fixed position. RESULTS: The oxygen isotope ratios of some international reference materials analyzed by the manual lasing technique were found to be isotopically lighter with wider variations in δ18 O values, whereas those measured by the automated lasing technique gave better reproducibility (less than 0.2‰, 2SD). The Δ17 O values, an excess of the δ17 O value relative to the fractionation line, also showed high reproducibility (±0.02‰, 2SD). CONCLUSIONS: The system described herein provides high-precision δ17 O and δ18 O measurements of silicate materials. The use of the automated lasing technique followed by careful and controlled purification procedures is preferred to achieve satisfactory isotopic ratio results.

A 300-Year High-Resolution Greenland Ice Record of Large-Scale Atmospheric Pollution by Arsenic in the Northern Hemisphere.

We report the first high-resolution record of arsenic (As) observed in Greenland snow and ice for the periods 1711-1970 and 2003-2009 AD. The results show well-defined large-scale atmospheric pollution by this toxic element in the northern hemisphere, beginning as early as the 18th century. The most striking feature is an abrupt, unprecedented enrichment factor (EF) peak in the late 1890s, with an ∼30-fold increase in the mean value above the Holocene natural level. Highly enriched As was evident until the late 1910s; a sharp decline was observed after the First World War, reaching a minimum in the early 1930s during the Great Depression. A subsequent increase lasted until the mid-1950s, before decreasing again. Comparisons between the observed variations and Cu smelting data indicate that Cu smelting in Europe and North America was the likely source of early anthropogenic As in Greenland. Despite a significant reduction of ∼80% in concentration and ∼60% in EF from the 1950s to the 2000s, more than 80% of present-day As in Greenland is of anthropogenic origin, probably due to increasing As emissions from coal combustion in China. This highlights the demand for the implementation of national and international environmental regulations to further reduce As emissions.

Short-term hearing results using ossicular replacement prostheses of hydroxyapatite versus titanium.

The aim of this study was to compare the short-term audiologic results of the ossiculoplasty using partial or total ossicular replacement prostheses (PORP or TORP) made of hydroxyapatite (HA) and titanium (Ti). Fifty-two consecutive patients who underwent ossiculoplasty due to chronic otitis media with or without cholesteatoma were enrolled. Patients were assessed at 6 months postoperatively to establish short-term audiologic results. Preoperative and postoperative air-conduction and bone-conduction thresholds were measured at five frequencies: 0.25, 0.5, 1, 2, and 3 kHz. Postoperative air-bone gap (ABG) of less than 20 dB was considered as successful. Success rates for HA PORP versus Ti PORP and HA TORP versus Ti TORP were compared. Postoperative ABGs at each frequency according to the types of prostheses were also compared. All types of prostheses showed a significant decrease of ABG postoperatively. Regarding PORP, the success rate of postoperative ABG of less than 20 dB was non-significantly higher in Ti group (89%) than in HA group (72%). Regarding TORP, HA group showed non-significantly higher success rate (100%) than Ti group (67%). Comparing postoperative ABGs at each frequency, there was no significant difference in ABGs between HA and Ti groups. There was no difference between the two materials. Both HA and Ti gave good functional results and operator can choose any types of prostheses by personal preference and affordability. Further randomized controlled long-term trials with large sample sizes are needed to establish the difference exactly.

Oxygen isotopic fractionation of O2 during adsorption and desorption processes using molecular sieve at low temperatures.

RATIONALE: Cryogenic trapping using molecular sieves is commonly used to collect O2 extracted from silicates for (17)O/(16)O and (18)O/(16)O analyses. However, gases which interfere with (17)O/(16)O analysis, notably NF3, are also trapped and their removal is essential for accurate direct measurement of the (17)O/(16)O ratio. It is also necessary to identify and quantify any isotopic fractionation associated with the use of cryogenic trapping using molecular sieves. METHODS: The oxygen isotopic compositions of O2 before and after desorption from, and adsorption onto, 13X and 5A molecular sieves (MS13X and MS5A) at 0°C, -78°C, -114°C, and -130°C were measured in order to determine the oxygen isotopic fractionation at these temperatures. We also investigated whether isotopic fractionation occurred when O2 gas was transferred sequentially into a second cold finger, also containing molecular sieve. RESULTS: It was confirmed that significant oxygen isotopic fractionation occurs between the gaseous O2 and that adsorbed onto molecular sieve, if desorption and adsorption are incomplete. As the fraction of released or untrapped O2 becomes smaller with decreasing trapping temperature (from 0 to -130°C), the isotopic fractionation becomes larger. Approximately half of the total adsorbed O2 is released from the molecular sieve during desorption at -114°C, which is the temperature recommended for separation from NF3 (retained on the molecular sieve), and this will interfere with (17)O/(16)O measurements. CONCLUSIONS: The use of a single cold finger should be avoided, because partial desorption is accompanied by oxygen isotopic fractionation, thereby resulting in inaccurate isotopic data. The use of a dual cold finger arrangement is recommended because, as we have confirmed, the transfer of O2 from the first trap to the second is almost 100%. However, even under these conditions, a small isotopic fractionation (0.18 ± 0.05‰ in δ(17)O values and 0.26 ± 0.06‰ in δ(18)O values) occurred, with O2 in the second trap being isotopically enriched in the heavier isotopes.

Implantable Multi-Cross-Linked Membrane-Ionogel Assembly for Reversible Non-Faradaic Neurostimulation.

Neural interfaces play a major role in modulating neural signals for therapeutic purposes. To meet the demand of conformable neural interfaces for developing bioelectronic medicine, recent studies have focused on the performance of electrical neurostimulators employing soft conductors such as conducting polymers and electronic or ionic conductive hydrogels. However, faradaic charge injection at the interface of the electrode and nerve tissue causes irreversible gas evolution, oxidation of electrodes, and reduction of biological ions, thus causing undesired tissue damage and electrode degradation. Here we report a conformable neural interface engineering based on multicross-linked membrane-ionogel assembly (termed McMiA), which enables nonfaradaic neurostimulation without irreversible charge transfer reaction. The McMiA consists of a genipin-cross-linked biopolymeric ionogel coupled with a dopamine-cross-linked graphene oxide membrane to prevent ion exchange between biological and synthetic McMiA ions and to function as a bioadhesive forming covalent bonds with the target tissues. In addition, the demonstration of bioelectronic medicine via the McMiA-based neurostimulation of sciatic nerves shows the enhanced clinical utility in treating the overactive bladder syndrome. As the McMiA-based neural interface is soft, robust for bioadhesion, and stable in a physiological environment, it can offer significant advancement in biocompatibility and long-term operability for neural interface engineering.

Noble gases and nitrogen in samples of asteroid Ryugu record its volatile sources and recent surface evolution.

The near-Earth carbonaceous asteroid (162173) Ryugu is expected to contain volatile chemical species that could provide information on the origin of Earth's volatiles. Samples of Ryugu were retrieved by the Hayabusa2 spacecraft. We measured noble gas and nitrogen isotopes in Ryugu samples and found that they are dominated by presolar and primordial components, incorporated during Solar System formation. Noble gas concentrations are higher than those in Ivuna-type carbonaceous (CI) chondrite meteorites. Several host phases of isotopically distinct nitrogen have different abundances among the samples. Our measurements support a close relationship between Ryugu and CI chondrites. Noble gases produced by galactic cosmic rays, indicating a ~5 million year exposure, and from implanted solar wind record the recent irradiation history of Ryugu after it migrated to its current orbit.

Complete Genome Sequence of Brevibacterium frigoritolerans Ant232, Isolated from Antarctic Snow.

We report the complete and circularized genome sequences of Brevibacterium frigoritolerans Ant232, generated using a combination of Illumina and PacBio platforms. The high-quality complete genome consists of a circular 5,586,945-bp chromosome and a 305,498-bp plasmid, with G+C contents of 40.66% and 36.8%, respectively.

Safe, Durable, and Sustainable Self-Powered Smart Contact Lenses.

Smart contact lenses have the potential to serve as noninvasive healthcare devices or virtual displays. However, their implementation is limited by the lack of suitable power sources for microelectronic devices. This Article demonstrates smart contact lenses with fully embedded glucose fuel cells that are safe, flexible, and durable against deformations. These fuel cells produced stable power throughout the day or during intermittent use after storage for weeks. When the lenses were exposed to 0.05 mM glucose solution, a steady-state maximum power density of 4.4 µW/cm2 was achieved by optimizing the chemistry and porous structure of the fuel cell components. Additionally, even after bending the lenses in half 100 times, the fuel cell performance was maintained without any mechanical failure. Lastly, when the fuel cells were connected to electroresponsive hydrogel capacitors, we could clearly distinguish between the tear glucose levels under normal and diabetic conditions through the naked eye.

Electrochemiluminescence in paired signal electrode (ECLipse) enables modular and scalable biosensing.

Electrochemiluminescence (ECL) has an inherently low background and enables precise chemical reactions through electrical control. Here, we report an advanced ECL system, termed ECLipse (ECL in paired signal electrode). We physically separated ECL generation from target detection: These two processes were carried out in isolated chambers and coupled through an electrode. The strategy allowed us to minimize cross-chemical reactions, design electrodes for high ECL signals, and integrate multiple sensors in a chip. As a proof of concept, we implemented an eight-plex ECLipse and applied it to detect host factors in human plasma. ECLipse achieved higher signal-to-noise ratio than conventional ECL assays and was >7000-fold more sensitive than enzyme-linked immunosorbent assay. In a pilot clinical study, we could detect septic conditions by measuring host factors [i.e., interleukin-3 (IL-3), IL-6, and procalcitonin (PCT)]. ECLipse assay further revealed distinct IL-3 and IL-6 patterns in patients with severe acute respiratory syndrome coronavirus 2 infection.

First asteroid gas sample delivered by the Hayabusa2 mission: A treasure box from Ryugu.

The Hayabusa2 spacecraft returned to Earth from the asteroid 162173 Ryugu on 6 December 2020. One day after the recovery, the gas species retained in the sample container were extracted and measured on-site and stored in gas collection bottles. The container gas consists of helium and neon with an extraterrestrial 3He/4He and 20Ne/22Ne ratios, along with some contaminant terrestrial atmospheric gases. A mixture of solar and Earth's atmospheric gas is the best explanation for the container gas composition. Fragmentation of Ryugu grains within the sample container is discussed on the basis of the estimated amount of indigenous He and the size distribution of the recovered Ryugu grains. This is the first successful return of gas species from a near-Earth asteroid.

Effect of Optical and Morphological Control of Single-Structured LEC Device.

We investigated the performance of single-structured light-emitting electrochemical cell (LEC) devices with Ru(bpy)3(PF6)2 polymer composite as an emission layer by controlling thickness and heat treatment. When the thickness was smaller than 120-150 nm, the device performance decreased because of the low optical properties and non-dense surface properties. On the other hand, when the thickness was over than 150 nm, the device had too high surface roughness, resulting in high-efficiency roll-off and poor device stability. With 150 nm thickness, the absorbance increased, and the surface roughness was low and dense, resulting in increased device characteristics and better stability. The heat treatment effect further improved the surface properties, thus improving the device characteristics. In particular, the external quantum efficiency (EQE) reduction rate was shallow at 100 °C, which indicates that the LEC device has stable operating characteristics. The LEC device exhibited a maximum luminance of 3532 cd/m2 and an EQE of 1.14% under 150 nm thickness and 100 °C heat treatment.

Artificial stimulus-response system capable of conscious response.

A stimulus-response system and conscious response enable humans to respond effectively to environmental changes and external stimuli. This paper presents an artificial stimulus-response system that is inspired by human conscious response and is capable of emulating it. The system is composed of an artificial visual receptor, artificial synapse, artificial neuron circuits, and actuator. By incorporating these artificial nervous components, a series of conscious response processes that markedly reduces response time as a result of learning from repeated stimuli are demonstrated. The proposed artificial stimulus-response system offers the promise of a new research field that would aid the development of artificial intelligence-based organs for patients with neurological disorders.

Visco-Poroelastic Electrochemiluminescence Skin with Piezo-Ionic Effect.

Following early research efforts devoted to achieving excellent sensitivity of electronic skins, recent design schemes for these devices have focused on strategies for transduction of spatially resolved sensing data into straightforward user-adaptive visual signals. Here, a material platform capable of transducing mechanical stimuli into visual readout is presented. The material layer comprises a mixture of an ionic transition metal complex luminophore and an ionic liquid (capable of producing electrochemiluminescence (ECL)) within a thermoplastic polyurethane matrix. The proposed material platform shows visco-poroelastic response to mechanical stress, which induces a change in the distribution of the ionic luminophore in the film, which is referred to as the piezo-ionic effect. This piezo-ionic effect is exploited to develop a simple device containing the composite layer sandwiched between two electrodes, which is termed "ECL skin". Emission from the ECL skin is examined, which increases with the applied normal/tensile stress. Additionally, locally applied stress to the ECL skin is spatially resolved and visualized without the use of spatially distributed arrays of pressure sensors. The simple fabrication and unique operation of the demonstrated ECL skin are expected to provide new insights into the design of materials for human-machine interactive electronic skins.

Stoichiometric Doping of Highly Coupled Cu2-xS Nanocrystal Assemblies.

The hole density of individual copper sulfide nanocrystals (Cu2-xS NCs) is determined from the stoichiometric mismatch (x) between copper and sulfide atoms. Consequently, the electronic properties of the material vary over a range of x. To exploit Cu2-xS NCs in devices, assemblies of NCs are typically required. Herein, we investigate the influence of x, referred to as the stoichiometric doping effect, on the structural, optical, electrical, and thermoelectric properties of electronically coupled Cu2-xS NC assemblies. The doping process is done by immersing the solid NC assemblies into a solution containing a Cu(I) complex for different durations (0-10 min). As Cu+ gradually occupied the copper-deficient sites of Cu2-xS NCs, x could be controlled from 0.9 to less than 0.1. Consequently, the near-infrared (NIR) absorbance of Cu2-xS NC assemblies changes systematically with x. With increasing x, electrical conductivity increased and the Seebeck coefficient decreased systematically, leading to the maximal thermoelectric power factor from a film of Cu2-xS NCs at an optimal doping condition yielding x = 0.1. The physical characteristics of the Cu2-xS NC assemblies investigated herein will provide guidelines for exploiting this emerging class of nanocrystal system based on doping.

Lead-Free Perovskite Nanocrystals for Light-Emitting Devices.

Lead halide perovskites with nanoscale geometries have received recent attention due to the defect-tolerant high photoluminescence quantum yield at tunable emission wavelengths and the possibility of room-temperature synthesis that does not compromise the physical properties of the materials. These characteristics offer opportunities to advance displays that cover the widest perceivable color. However, lead toxicity obstructs the commercialization of this technology. Therefore, recent efforts have investigated lead-free halide perovskite nanocrystals. Here, we provide our perspectives on the most exciting achievements in the materials design and photophysical properties of lead-free perovskite nanocrystals, particularly for applications in light-emitting devices. This Perspective includes a short summary on the characteristic features of halide perovskite nanocrystals; discussion on the candidate elements to replace lead; methods to prepare colloidal lead-free perovskite nanocrystals; methods to control and enhance the optical properties; a recent demonstration of utilizing lead-free perovskite nanocrystals in light-emitting devices; and an outlook on the field.

Dynamic Interplay between Transport and Reaction Kinetics of Luminophores on the Operation of AC-Driven Electrochemiluminescence Devices.

Electrochemiluminescence (ECL) involves light emission accompanied by a series of electrochemical processes on luminophores, which has been recently exploited in a new light-emitting device platform, referred to as the ECL device (ECLD). Here, we investigate the influence of the transport of the ECL luminophores and their reaction kinetics on the emission properties of alternating current-voltage-driven ECLDs. A model based on the diffusion and reaction rate equations is developed to predict the operational frequency ( f)-dependent luminance properties of the ECLD. It is found that more frequent generation of the redox precursors with a shorter time interval enhances their probability of encountering each other, and therefore the luminance of the device increases with increasing f initially. The luminance at a higher f, however, is suppressed eventually due to the decreased rate of the electrode reactions. Using the model, the influence of diffusion and reaction rates on the performance of an ECLD is analyzed separately and systematically. The results provide insight on the operation of this emerging class of a light-emitting device platform.

Comparing rock-inhabiting microbial communities in different rock types from a high arctic polar desert.

Although rocks are habitable places for microbes in extreme environments, microbial diversity in these lithic environments is still poorly understood. The diversity and abundance of rock-inhabiting microbial communities in different types of rock in Svalbard, Norwegian High Arctic were examined using NGS sequencing of bacterial 16S rRNA genes and fungal 28S rRNA genes. Compositions of both bacterial and fungal communities varied across different rock types: sandstone, limestone, basalt, granite and travertine. Bacterial communities were dominated by Actinobacteria, Proteobacteria, Chloroflexi, Bacteroidetes and Acidobacteria. Fungal communities consisted of Eurotiomycetes, Lecanoromycetes, Dothideomycetes and Leotiomycetes. Both bacterial and fungal community compositions were significantly correlated with the geochemical characteristics of rocks. Bacterial communities were considerably correlated with the rock elements such as Mg and Ca. Fungal communities were considerably correlated with Fe. Interestingly, many dominant bacterial and fungal operational taxonomic units in the investigated rocks from the study area were closely affiliated to those found in other cold regions such as Alpine area, Arctic and Antarctica, suggesting that environmental constraints such as cold temperature may lead to convergence in microbial community composition. These results confirm that rocks in cold environments act as reservoirs of diverse bacteria and fungi, which may improve our understanding of lithic microbial ecology in the cold desert.

Second cancer incidence and risk factors in patients with salivary gland cancers.

IMPORTANCE: Second primary cancers (SPCs) are common in patients with head and neck squamous cell carcinoma, while the incidence and risk factors of SPC in patients with salivary gland cancers (SGCs) are largely unknown. This study aimed to examine the incidence of and risk factors for SPC in patients with SGC. OBJECTIVE: To report the risk factors and incidence of SPC in patients with SGC and compare them with the values of newly developed cancers (NDCs) in a healthy population. DESIGN, SETTING, AND PARTICIPANTS: A retrospective case-control study conducted at a university teaching hospital. The study population comprised 184 patients with SGC, without a history of cancer, who were treated between 2000 and 2010 and followed up for at least 2 years, and 200 healthy individuals (control group) who underwent medical examinations in health promotion programs during the same period. INTERVENTIONS: All individuals received the diagnostic scrutiny including endoscopic and radiological examinations at initial staging and at follow-up. Individuals suspected of having SPC or NDC underwent histological confirmation. MAIN OUTCOMES AND MEASURES: Risk factors of SPC development and cumulative incidence of SPC (or NDC) in each group. RESULTS: The cumulative 2-, 5-, and 10-year rates of SPC were 4.4%, 8.3%, and 12.4%, respectively, and those of NDC were 1.1%, 3.4%, and 10.5%, respectively (P = .29). Except for the thyroid gland, SPC and NDC were located outside the head and neck region. Univariate analysis was unable to identify any variable significantly predictive of SPC or NDC. CONCLUSIONS AND RELEVANCE: In the present study, there was no statistical difference in the SPC cumulative incidence between the SGC and control groups, which might result from the possible limitation of a small sample size.

Chelyabinsk airburst, damage assessment, meteorite recovery, and characterization.

The asteroid impact near the Russian city of Chelyabinsk on 15 February 2013 was the largest airburst on Earth since the 1908 Tunguska event, causing a natural disaster in an area with a population exceeding one million. Because it occurred in an era with modern consumer electronics, field sensors, and laboratory techniques, unprecedented measurements were made of the impact event and the meteoroid that caused it. Here, we document the account of what happened, as understood now, using comprehensive data obtained from astronomy, planetary science, geophysics, meteorology, meteoritics, and cosmochemistry and from social science surveys. A good understanding of the Chelyabinsk incident provides an opportunity to calibrate the event, with implications for the study of near-Earth objects and developing hazard mitigation strategies for planetary protection.