Stratum-Confined Solid-State Reaction (SC-SSR) toward Colloidal Silicon-Based Hollow Nanostructures for Bioapplications.

Silicon nanostructures (SiNSs) can provide multifaceted bioapplications; but preserving their subhundred nm size during high-temperature silica-to-silicon conversion is the major bottleneck. The SC-SSR utilizes an interior metal-silicide stratum space at a predetermined radial distance inside silica nanosphere to guide the magnesiothermic reduction reaction (MTR)-mediated synthesis of hollow and porous SiNSs. In depth mechanistic study explores solid-to-hollow transformation encompassing predefined radial boundary through the participation of metal-silicide species directing the in-situ formed Si-phase accumulation within the narrow stratum. Evolving thin-porous Si-shell remains well protected by the in-situ segregated MgO emerging as a protective cast against the heat-induced deformation and interparticle sintering. Retrieved hydrophilic SiNSs (<100 nm) can be conveniently processed in different biomedia as colloidal solutions and endocytosized inside cells as photoluminescence (PL)-based bioimaging probes. Inside the cell, rattle-like SiNSs encapsulated with Pd nanocrystals can function as biorthogonal nanoreactors to catalyze intracellular synthesis of probe molecules through C-C cross coupling reaction.

Tailoring Binding Abilities by Incorporating Oxophilic Transition Metals on 3D Nanostructured Ni Arrays for Accelerated Alkaline Hydrogen Evolution Reaction.

Developing efficient and inexpensive electrocatalysts for the hydrogen evolution reaction (HER) in alkaline water electrolysis plays a key role for renewable hydrogen energy technology. The slow reaction kinetics of HER in alkaline solutions, however, has hampered advances in high-performance hydrogen production. Herein, we investigated the trends in HER activity with respect to the binding energies of Ni-based thin film catalysts by incorporating a series of oxophilic transition metal atoms. It was found that the doping of oxophilic atoms enables the modulation of binding abilities of hydrogen and hydroxyl ions on the Ni surfaces, leading to the first establishment of a volcano relation between OH-binding energies and alkaline HER activities. In particular, Cr-incorporated Ni catalyst shows optimized OH-binding as well as H-binding energies for facilitating water dissociation and improving HER activity in alkaline media. Further enhancement of catalytic performance was achieved by introducing an array of three-dimensional (3D) Ni nanohelixes (NHs) that provide abundant surface active sites and effective channels for charge transfer and mass transport. The Cr dopants incorporated into the Ni NHs accelerate the dissociative adsorption process of water, resulting in remarkably enhanced catalytic activities in alkaline medium. Our approach can provide a rational design strategy and experimental methodology toward efficient bimetallic electrocatalysts for alkaline HER using earth-abundant elements.

ZnFe2 O4 Dendrite/SnO2 Helix 3D Hetero-Structure Photoanodes for Enhanced Photoelectrochemical Water Splitting: Triple Functions of SnO2 Nanohelix.

An array of SnO2 nanohelix structures is employed to fabricate a SnO2 helix@ZnFe2 O4 dendrite core-shell 3D heterostructure photoanode for photoelectrochemical (PEC) water splitting. The SnO2 helix provides triple critical functions to enhance the PEC performance of the photoanode. First, it scatters the incident light to achieve a higher light harvesting efficiency. Second, it provides a facile electron pathway as an electron transfer layer (ETL) while blocking hole transport to mitigate charge recombination in the bulk of ZnFe2 O4 . Finally, it becomes a template for the formation of ZnFe2 O4 dendrite nanostructure shell. The ZnFe2 O4 dendrite/SnO2 helix photoanode exhibits a remarkable increase in incident photon-to-electron conversion efficiency compared to unmodified ZnFe2 O4 with no ETL and modified one with "flat" SnO2 ETL. The surface of the ZnFe2 O4 /SnO2 helix photoanode is further modified with TiO2 passivation layer and NiFeOx oxygen evolution co-catalyst to achieve one of the best PEC performances among reported ZnFe2 O4 -based photoanodes.

Appropriateness of task of public health doctors in South Korea.

INTRODUCTION: Public health doctors (PHDs) in South Korea serve the medically underserved region of South Korea as part of national service duty, but their number has declined in recent years (due to changes in the medical education system). Therefore, there is an increasing need to deploy PHDs efficiently. Consisting of 2138 medical doctors of different specialties, they serve as both primary care physicians and public health experts. METHODS: The purpose of this study was to investigate the appropriateness of tasks of PHDs in South Korea. RESULTS: Of the 2138 PHDs invited, 1015 participated in the survey. Most PHDs performed primary care and vaccination duties (96.8% and 85.8%). PHDs evaluated the appropriateness of tasks and number of PHDs as above the midpoint of a five-point Likert scale (3.5±1.1 and 3.4±1.1). The majority of offices were located within 5 km of private clinics and hospitals (72.7% and 45.2%). CONCLUSIONS: PHDs on remote islands highly value the validity and deployment needs of PHDs, while PHDs in close proximity to private clinics or hospitals give a low score. This suggests that there is a need to more efficiently deploy PHDs depending on local characteristics and the presence or absence of nearby private medical clinics and hospitals.

Efficient Alkaline Hydrogen Evolution Reaction Using Superaerophobic Ni Nanoarrays with Accelerated H2 Bubble Release.

Despite the adverse effects of H2 bubbles adhering to catalyst's surface on the performance of water electrolysis, the mechanisms by which H2 bubbles are effectively released during the alkaline hydrogen evolution reaction (HER) remain elusive. In this study, a systematic investigation on the effect of nanoscale surface morphologies on H2 bubble release behaviors and HER performance by employing earth-abundant Ni catalysts consisting of an array of Ni nanorods (NRs) with controlled surface porosities is performed. Both aerophobicity and hydrophilicity of the catalyst's surface vary according to the surface porosity of catalysts. The Ni catalyst with the highest porosity of ≈52% exhibits superaerophobic nature as well as the best HER performance among the Ni catalysts. It is found that the Ni catalyst's superaerophobicity combined with the effective open pore channels enables the accelerated release of H2 bubbles from the surface, leading to a significant improvement in geometric activities, particularly at high current densities, as well as intrinsic activities including both specific and mass activities. It is also demonstrated that the superaerophobicity enabled by highly porous Ni NRs can be combined with Pt and Cr having optimal binding abilities to further optimize electrocatalytic performance.

Enhancing durability of automotive fuel cells via selective electrical conductivity induced by tungsten oxide layer coated directly on membrane electrode assembly.

The poor durability, attributed to catalyst corrosion during start-up/shutdown (SU/SD), is a major obstacle to the commercialization of fuel cell electric vehicles (FCEVs). We recently achieved durability enhancement under SU/SD conditions by implementing a metal-insulator transition (MIT) using proton intercalation/deintercalation in WO3. However, such oxide-supported catalysts were unsuitable for direct application to the mass production stage of membrane electrode assembly (MEA) process due to their physical and chemical properties. Here, we report a unique approach that achieves the same durability enhancement in SU/SD situations while being directly applicable to the conventional MEA fabrication process. We coated WO3 on the bipolar plate, gas diffusion layer, and MEA to investigate whether the MIT phenomenon was realized. The WO3-coated MEA demonstrated 94% performance retention during SU/SD, the highest level to our knowledge. It can directly contribute to enhancing the durability of commercial FCEVs and be immediately applied to the MEA mass production process.

Exploring Autonomic Alterations during Seizures in Temporal Lobe Epilepsy: Insights from a Heart-Rate Variability Analysis.

Epilepsy's impact on cardiovascular function and autonomic regulation, including heart-rate variability, is complex and may contribute to sudden unexpected death in epilepsy (SUDEP). Lateralization of autonomic control in the brain remains the subject of debate; nevertheless, ultra-short-term heart-rate variability (HRV) analysis is a useful tool for understanding the pathophysiology of autonomic dysfunction in epilepsy patients. A retrospective study reviewed medical records of patients with temporal lobe epilepsy who underwent presurgical evaluations. Data from 75 patients were analyzed and HRV indices were extracted from electrocardiogram recordings of preictal, ictal, and postictal intervals. Various HRV indices were calculated, including time domain, frequency domain, and nonlinear indices, to assess autonomic function during different seizure intervals. The study found significant differences in HRV indices based on hemispheric laterality, language dominancy, hippocampal atrophy, amygdala enlargement, sustained theta activity, and seizure frequency. HRV indices such as the root mean square of successive differences between heartbeats, pNN50, normalized low-frequency, normalized high-frequency, and the low-frequency/high-frequency ratio exhibited significant differences during the ictal period. Language dominancy, hippocampal atrophy, amygdala enlargement, and sustained theta activity were also found to affect HRV. Seizure frequency was correlated with HRV indices, suggesting a potential relationship with the risk of SUDEP.

A zero-dimensional predictive model for the pressure drop in the stenotic coronary artery based on its geometric characteristics.

The diameter- or area-reduction ratio measured from coronary angiography, commonly used in clinical practice, is not accurate enough to represent the functional significance of the stenosis, i.e., the pressure drop across the stenosis. We propose a new zero-dimensional model for the pressure drop across the stenosis considering its geometric characteristics and flow rate. To identify the geometric parameters affecting the pressure drop, we perform three-dimensional numerical simulations for thirty-three patient-specific coronary stenoses. From these numerical simulations, we show that the pressure drop is mostly determined by the curvature as well as the area-reduction ratio of the stenosis before the minimal luminal area (MLA), but heavily depends on the area-expansion ratio after the MLA due to flow separation. Based on this result, we divide the stenosis into the converging and diverging parts in the present zero-dimensional model. The converging part is segmented into a series of straight and curved pipes with curvatures, and the loss of each pipe is estimated by an empirical relation between the total pressure drop, flow rate, and pipe geometric parameters (length, diameter, and curvature). The loss in the diverging part is predicted by a relation among the total pressure drop, Reynolds number, and area expansion ratio with the coefficients determined by a machine learning method. The pressure drops across the stenoses predicted by the present zero-dimensional model agree very well with those obtained from three-dimensional numerical simulations.

Engineering of a Biomimetic Pericyte-Covered 3D Microvascular Network.

Pericytes enveloping the endothelium play an important role in the physiology and pathology of microvessels, especially in vessel maturation and stabilization. However, our understanding of fundamental pericyte biology is limited by the lack of a robust in vitro model system that allows researchers to evaluate the interactions among multiple cell types in perfusable blood vessels. The present work describes a microfluidic platform that can be used to investigate interactions between pericytes and endothelial cells (ECs) during the sprouting, growth, and maturation steps of neovessel formation. A mixture of ECs and pericytes was attached to the side of a pre-patterned three dimensional fibrin matrix and allowed to sprout across the matrix. The effects of intact coverage and EC maturation by the pericytes on the perfused EC network were confirmed using a confocal microscope. Compared with EC monoculture conditions, EC-pericyte co-cultured vessels showed a significant reduction in diameter, increased numbers of junctions and branches and decreased permeability. In response to biochemical factors, ECs and pericytes in the platform showed the similar features with previous reports from in vivo experiments, thus reflect various pathophysiological conditions of in vivo microvessels. Taken together, these results support the physiological relevancy of our three-dimensional microfluidic culture system but also that the system can be used to screen drug effect on EC-pericyte biology.