Atomically dispersed hexavalent iridium oxide from MnO2 reduction for oxygen evolution catalysis.

Hexavalent iridium (IrVI) oxide is predicted to be more active and stable than any other iridium oxide for the oxygen evolution reaction in acid; however, its experimental realization remains challenging. In this work, we report the synthesis, characterization, and application of atomically dispersed IrVI oxide (IrVI-ado) for proton exchange membrane (PEM) water electrolysis. The IrVI-ado was synthesized by oxidatively substituting the ligands of potassium hexachloroiridate(IV) (K2IrCl6) with manganese oxide (MnO2). The mass-specific activity (1.7 × 105 amperes per gram of iridium) and turnover number (1.5 × 108) exceeded those of benchmark iridium oxides, and in situ x-ray analysis during PEM operations manifested the durability of IrVI at current densities up to 2.3 amperes per square centimeter. The high activity and stability of IrVI-ado showcase its promise as an anode material for PEM electrolysis.

Characteristic craniofacial defects associated with a novel USP9X truncation mutation.

Germline loss-of-function mutations in USP9X have been reported to cause a wide spectrum of congenital anomalies. Here, we report a Japanese girl with a novel heterozygous nonsense mutation in USP9X who exhibited intellectual disability with characteristic craniofacial abnormalities, including hypotelorism, brachycephaly, hypodontia, micrognathia, severe dental crowding, and an isolated submucous cleft palate. Our findings provide further evidence that disruptions in USP9X contribute to a broad range of congenital craniofacial abnormalities.

Exploring the association between number of teeth, food intake, and cognitive function: A 9-year longitudinal study.

OBJECTIVES: This study aimed to investigate the association between the number of teeth, food intake, and cognitive function in Japanese community-dwelling older adults. METHODS: This 9-year longitudinal study included a total of 293 analyzable participants who participated in baseline and follow-up surveys. Dental status (number of teeth and periodontal pocket depth), dietary assessment using the brief-type self-administered diet history questionnaire, cognitive function, and the following confounding factors were evaluated: educational level, financial satisfaction, living situation, smoking and drinking habits, history of chronic diseases, apolipoprotein E-ε4 carrier, body mass index, handgrip strength, instrumental activities of daily living, and depressive symptomatology. The Japanese version of the Montreal Cognitive Assessment was used to evaluate cognitive function. A multinomial logistic regression analysis for the intake level of each food categorized into three groups (low, moderate, high), and a generalized estimating equation (GEE) for cognitive function over nine years were performed. RESULTS: After controlling for confounding factors, the number of teeth was shown to be associated with the intake of green-yellow vegetables and meat. Furthermore, the GEE indicated that the lowest quartile of intake of green-yellow vegetables significantly associated with lower cognitive function (unstandardized regression coefficient [B] = -0.96, 95 % confidence interval [CI]: -1.72 to -0.20), and the lowest quartile of intake of meat significantly associated with lower cognitive function (B = -1.42, 95 % CI: -2.27 to -0.58). CONCLUSIONS: The intake of green and yellow vegetables and meat, which is influenced by the number of teeth, was associated with cognitive function in Japanese community-dwelling older adults. CLINICAL SIGNIFICANCE: There are few studies that have examined the association between oral health, food intake, and cognitive function. This 9-year longitudinal study suggests that it is important to maintain natural teeth to enable the functional means to consume green-yellow vegetables and meat, and thereby help maintain cognitive function.

The relationship between changes in occlusal support and masticatory performance using 6-year longitudinal data from the SONIC study.

OBJECTIVES: Reduced occlusal support is thought to be related to a decline in masticatory performance. However, previous research in this field was based on cross-sectional studies. In this study, we conducted a 6-year longitudinal observation of older adults living in the community and examined the associations of changes in occlusal support with masticatory performance. METHODS: Of the 864 participants aged 72-74 years in the SONIC study, 488 who were followed up (median follow-up period 5.92 years) and had no missing data were included in this study. Participants were divided into three groups according to the number of occlusal support zones in the posterior area: Complete occlusion (four zones), Reduced occlusion (one to three zones), and Collapsed occlusion (no occlusal support zone). Longitudinal analysis of the relationship between occlusal support and masticatory performance was undertaken with linear mixed-effects models. RESULTS: Sex, occlusal force, number of unreplaced missing teeth, aging, and occlusal support change were significantly related to masticatory performance. Furthermore, the interaction term between change in occlusal support and aging was a significant explanatory variable for the decline in masticatory performance. The interaction was strongest in the group that changed from Complete or Reduced occlusion to Collapsed occlusion. This result indicates that the loss of occlusal support is a major factor contributing to declining masticatory performance. CONCLUSIONS: The decline of occlusal support was greatly associated with the deterioration of masticatory performance. Our results suggest that older adults need to prevent the collapse of posterior occlusal support to maintain their masticatory performance. CLINICAL SIGNIFICANCE: Occlusal support is important for preserving masticatory performance in older adults. Preventing the loss of molars and retaining occlusal support may contribute to maintaining food intake diversity and nutritional status, thereby improving quality of life. Dental professionals need to carefully examine dental status to assess the risk of occlusal collapse.

Relationship between the number of teeth, occlusal force, occlusal contact area, and dietary hardness in older Japanese adults: The SONIC study.

PURPOSE: Individuals with impaired masticatory function tend to prefer soft foods, which results in decreased masticatory muscle activity. This study examined the association between the oral condition (number of teeth, occlusal force, and occlusal contact area) and dietary hardness using a daily dietary questionnaire. METHODS: This cross-sectional study evaluated 1841 participants aged 69-71 and 79-81 years. Registered dentists examined the number of teeth, occlusal force, and occlusal contact area. Dietary hardness was defined as the estimated masticatory muscle activity required for a habitual diet. Habitual diet during the preceding month was assessed using a brief self-administered diet history questionnaire. Confounding factors, such as age, sex, socioeconomic status, smoking habits, history of chronic diseases (hypertension, hyperlipidemia, and diabetes), and cognitive function were also evaluated. Multivariate linear regression analyses were performed to assess the association between dietary hardness and each oral condition. RESULTS: Occlusal force (standardized regression coefficients [ß]=0.08, P < 0.01) and occlusal contact area (ß=0.06, P < 0.01) were significantly associated with dietary hardness after adjusting for the confounding factors. Number of teeth was not significantly associated with dietary hardness. In addition, the associations between dietary hardness, sex, and a history of diabetes were stronger than those between dietary hardness and oral factors. CONCLUSIONS: Occlusal force and contact area were significantly associated with dietary hardness as estimated from the masticatory muscle activity using a daily diet questionnaire.

Emergence of Dynamically-Disordered Phases During Fast Oxygen Deintercalation Reaction of Layered Perovskite.

Determination of a reaction pathway is an important issue for the optimization of reactions. However, reactions in solid-state compounds have remained poorly understood because of their complexity and technical limitations. Here, using state-of-the-art high-speed time-resolved synchrotron X-ray techniques, the topochemical solid-gas reduction mechanisms in layered perovskite Sr3 Fe2 O7- δ (from δ ∼ 0.4 to δ = 1.0), which is promising for an environmental catalyst material is revealed. Pristine Sr3 Fe2 O7- δ shows a gradual single-phase structural evolution during reduction, indicating that the reaction continuously proceeds through thermodynamically stable phases. In contrast, a nonequilibrium dynamically-disordered phase emerges a few seconds before a first-order transition during the reduction of a Pd-loaded sample. This drastic change in the reaction pathway can be explained by a change in the rate-determining step. The synchrotron X-ray technique can be applied to various solid-gas reactions and provides an opportunity for gaining a better understanding and optimizing reactions in solid-state compounds.

Cytosolic protein delivery using ultrasound-guided vaporization of perfluorocarbon nano-droplets.

Ultrasound-guided protein delivery is promising for site-specific control of cellular functions in the deep interior of the body in a noninvasive manner. Herein, we propose a method for cytosolic protein delivery based on ultrasound-guided intracellular vaporization of perfluorocarbon nano-droplets. The nano-droplets were conjugated with cargo proteins through a bio-reductively cleavable linker and introduced into living cells via antibody-mediated binding to a cell-surface receptor, which gets internalized through endocytosis. After the cells were exposed to ultrasound for endosomal escape of proteins, the ultrasound-responsive cytosolic release of a cargo enzyme was confirmed by visualizing the hydrolysis of the fluorogenic substrate using confocal microscopy. Moreover, a significant decrease in cell viability was achieved via the release of a cytotoxic protein in response to ultrasound treatment. The results of this study provide the proof of a principle that protein-conjugated nano-droplets can be used as carriers in ultrasound-guided cytosolic delivery of proteins.

Relationship between occlusal force and psychological frailty in Japanese community-dwelling older adults: The Septuagenarians, Octogenarians, Nonagenarians Investigation with Centenarians study.

BACKGROUND: Frailty increases the risk of negative health-related events, such as falls, disability, hospitalizations, and death. Although the association between oral health and physical frailty is well established, the relationship between oral health and psychological frailty has not yet been investigated. Therefore, we conducted a cross-sectional study to examine the association between maximal occlusal force and psychological frailty in Japanese community-dwelling older adults. METHODS: Psychological frailty was defined as a World Health Organization-5 scale (WHO-5) score of <13, cognitive and functional status was defined as a Japanese version of the Montreal Cognitive Assessment (MoCA-J) score of <23, and psychological robustness was defined as a WHO-5 score of ≥13 and a MoCA-J score of ≥23. We used a cross-sectional study design to measure maximal occlusal force in 1810 participants, and examined the following factors relevant to psychological frailty: educational level, financial status, living situation, history of chronic diseases, handgrip strength, and instrumental activities of daily living. We used propensity score matching to match the psychological frailty and psychological robustness groups according to demographic and confounding factors. This process, resulted in 344 participants, of whom 172 were in the psychological frailty group and 172 were in the psychological robustness group. In the matched cohort, differences between groups with and without psychological frailty were compared using generalized estimating equations for maximal occlusal force after adjusting for the number of teeth. RESULTS: After controlling for potential confounding factors of frailty, the psychological frailty group showed lower maximal occlusal force compared with the psychological robustness group (unstandardized regression coefficients = -72.7, 95% confidence interval: -126.3 to -19.1). CONCLUSIONS: Maximal occlusal force was associated with a reduced prevalence of psychological frailty among Japanese community-dwelling older adults participating in our study.

Application of High-Energy-Resolution X-ray Absorption Spectroscopy at the U L3-Edge to Assess the U(V) Electronic Structure in FeUO4.

FeUO4 was studied to clarify the electronic structure of U(V) in a metal monouranate compound. We obtained the peak splitting of spectra utilizing high-energy-resolution fluorescence detection-X-ray absorption near-edge structure (HERFD-XANES) spectroscopy at the U L3-edge, which is a novel technique in uranium(V) monouranate compounds. Theoretical calculations revealed that the peak splitting was caused by splitting of the 6d orbital of U(V) in FeUO4, which would be used to detect minor U(V) species. Such distinctive electronic states are of major interest to researchers and engineers working in various fields, from fundamental physics to the nuclear industry and environmental sciences for actinide elements.

Predictive factors for tooth loss in older adults vary according to occlusal support: A 6-year longitudinal survey from the SONIC study.

OBJECTIVES: The aim of this cohort study among community-dwelling older adults aged over 70 years was to investigate the influence of occlusal support on tooth loss, and to determine predictive factors for tooth loss for each occlusal support category using multilevel analyses. METHODS: Participants were 812 older adults who completed the baseline survey and the follow-up survey 6 years later. The Eichner index was used to evaluate occlusal support status. A generalized estimating equation (GEE) logistic regression analysis was used to examine the influence of occlusal support status on tooth loss while adjusting for various factors at individual and tooth levels. Similar analyses were separately performed in each Eichner class to determine predictive factors for tooth loss. RESULTS: The GEE showed that a decline in occlusal support increased the risk of tooth loss (Eichner A: reference category, Eichner B: odds ratio (OR) = 1.96, p < 0.001, Eichner C: OR = 3.04, p < 0.001). Stratified analysis showed that deeper periodontal pockets and abutment teeth for fixed partial dentures were significantly associated with tooth loss, regardless of occlusal support. In Eichner A, the presence of an opposing tooth was advantageous in protecting the tooth, and a missing adjacent tooth was not significantly associated with tooth loss. An opposing tooth was associated with the risk of tooth loss in Eichner B, and a missing adjacent tooth was significantly associated with tooth loss in Eichner B and C. CONCLUSIONS: A decline in occlusal support accelerated tooth loss. Predictive factors for tooth loss varied depending on occlusal support status. CLINICAL SIGNIFICANCE: Occlusal support is an important factor in preventing tooth loss. Dentition conditions such as missing adjacent teeth and the presence of opposing teeth increase the risk of tooth loss in participants with poor occlusal support. Dental personnel need to carefully examine dentition conditions to assess the risk of occlusal collapse.

Operando Imaging of Ce Radical Scavengers in a Practical Polymer Electrolyte Fuel Cell by 3D Fluorescence CT-XAFS and Depth-Profiling Nano-XAFS-SEM/EDS Techniques.

There is little information on the spatial distribution, migration, and valence of Ce species doped as an efficient radical scavenger in a practical polymer electrolyte fuel cell (PEFC) for commercial fuel cell vehicles (FCVs) closely related to a severe reliability issue for long-term PEFC operation. An in situ three-dimensional fluorescence computed tomography-X-ray absorption fine structure (CT-XAFS) imaging technique and an in situ same-view nano-XAFS-scanning electron microscopy (SEM)/energy-dispersive spectrometry (EDS) combination technique were applied for the first time to perform operando spatial visualization and depth-profiling analysis of Ce radical scavengers in a practical PEFC of Toyota MIRAI FCV under PEFC operating conditions. Using these in situ techniques, we successfully visualized and analyzed the domain, density, valence, and migration of Ce scavengers that were heterogeneously distributed in the components of PEFC, such as anode microporous layer, anode catalyst layer, polymer electrolyte membrane (PEM), cathode catalyst layer, and cathode microporous layer. The average Ce valence states in the whole PEFC and PEM were 3.9+ and 3.4+, respectively, and the Ce3+/Ce4+ ratios in the PEM under H2 (anode)-N2 (cathode) at an open-circuit voltage (OCV), H2-air at 0.2 A cm-2, and H2-air at 0.0 A cm-2 were 70 ± 5:30 ± 5%, as estimated by both in situ fluorescence CT-X-ray absorption near-edge spectroscopy (XANES) and nano-XANES-SEM/EDS techniques. The Ce3+ migration rates in the electrolyte membrane toward the anode and cathode electrodes ranged from 0.3 to 3.8 µm h-1, depending on the PEFC operating conditions. Faster Ce3+ migration was not observed with voltage transient response processes by highly time-resolved (100 ms) and spatially resolved (200 nm) nano-XANES imaging. Ce3+ ions were suggested to be coordinated with both Nafion sulfonate (Nfsul) groups and water to form [Ce(Nfsul)x(H2O)y]3+. The Ce migration behavior may also be affected by the spatial density of Ce, interactions of Ce with Nafion, thickness and states of the PEM, and H2O convection, in addition to the PEFC operating conditions. The unprecedented operando imaging of Ce radical scavengers in the practical PEFCs by both in situ three-dimensional (3D) fluorescence CT-XAFS imaging and in situ depth-profiling nano-XAFS-SEM/EDS techniques yields intriguing insights into the spatial distribution, chemical states, and behavior of Ce scavengers under the working conditions for the development of next-generation PEFCs with high long-term reliability and durability.

Decline of oral functions in old-old adults and their relationship with age and sex: The SONIC study.

BACKGROUND: Many physical functions decline with aging, but it is not known whether oral functions vary according to sex or decline with aging, as it occurs with physical functions. The present study aimed to examine the association of sex, age, and elapsed years with occlusal force and tongue pressure using a generalized linear mixed-effect model (GLMM) over a 3-year period among old-old Japanese adults. METHODS: Participants were community-dwelling older adults who participated in a survey (June 2014-March 2017) and a follow-up survey (July 2017-December 2019) after 3 years (n = 951: 70-year group, n = 466; 80-year group, n = 391; 90-year group, n = 94). Dental examinations including the number of teeth, occlusal force, and tongue pressure were conducted, and a GLMM was used to estimate the association of sex, age, and elapsed years with occlusal force and tongue pressure, adjusting for the number of teeth. RESULTS: The GLMM showed that occlusal force was significantly associated with sex (reference; male, non-standardized coefficient: B = -66.9 [female], p < 0.001), age (reference; 70-year group, B = -81.7 [80-year group], p < 0.001, B = -87.2 [90-year group], p < 0.001), and the number of teeth (B = 13.8, p < 0.001), but did not significantly decrease with elapsed years. Tongue pressure was significantly associated with sex (reference; male, B = -0.94 [female], p = 0.034) and age (reference; 70-year group, B = -1.78 [80-year group], p < 0.001, B = -5.47 [90-year group], p < 0.001). Tongue pressure decreased significantly with elapsed years (B = -0.82, p < 0.001). CONCLUSIONS: These findings suggest that tongue pressure significantly decreased over time, but occlusal force did not. Tongue-related muscles may be more susceptible to aging than masticatory muscles.

Oral Functions Are Associated with Muscle Strength and Physical Performance in Old-Old Japanese.

Grip strength and walking speed are considered to be important indicators of physical frailty. However, no study has contemporaneously examined any association of multiple oral functions with grip strength and walking speed. The purpose of this study was to examine which oral functions are associated with muscle strength (grip strength), physical performance (walking speed) or both. The study participants were 511 community-dwelling people (254 men and 257 women) aged 77-81 years old. Six oral functions-oral wetness, occlusal force, tongue-lip motor function, tongue pressure, masticatory performance and swallowing function-were measured. Grip strength and walking speed were also measured. A partial correlation analysis, adjusted for gender, showed that occlusal force, tongue-lip motor function, masticatory performance and swallowing function were significantly associated with both grip strength and walking speed. In addition, tongue pressure was significantly associated with grip strength. A general linear model showed that tongue pressure and occlusal force were significantly associated with grip strength. Swallowing function and tongue-lip motor function were significantly associated with walking speed. It is suggested that there are different oral function measures for muscle strength and physical performance, and these oral function measures could be a useful proxy for physical frailty.

Single-Atom High-Temperature Catalysis on a Rh1O5 Cluster for Production of Syngas from Methane.

Single-atom catalysts are a relatively new type of catalyst active for numerous reactions but mainly for chemical transformations performed at low or intermediate temperatures. Here we report that singly dispersed Rh1O5 clusters on TiO2 can catalyze the partial oxidation of methane (POM) at high temperatures with a selectivity of 97% for producing syngas (CO + H2) and high activity with a long catalytic durability at 650 °C. The long durability results from the substitution of a Ti atom of the TiO2 surface lattice by Rh1, which forms a singly dispersed Rh1 atom coordinating with five oxygen atoms (Rh1O5) and an undercoordinated environment but with nearly saturated bonding with oxygen atoms. Computational studies show the back-donation of electrons from the dz2 orbital of the singly dispersed Rh1 atom to the unoccupied orbital of adsorbed CHn (n > 1) results in the charge depletion of the Rh1 atom and a strong binding of CHn to Rh1. This strong binding decreases the barrier for activating C-H, thus leading to high activity of Rh1/TiO2. A cationic Rh1 single atom anchored on TiO2 exhibits a weak binding to atomic carbon, in contrast to the strong binding of the metallic Rh surface to atomic carbon. The weak binding of atomic carbon to Rh1 atoms and the spatial isolation of Rh1 on TiO2 prevent atomic carbon from coupling on Rh1/TiO2 to form carbon layers, making Rh1/TiO2 resistant to carbon deposition than supported metal catalysts for POM. The highly active, selective, and durable high-temperature single-atom catalysis performed at 650 °C demonstrates an avenue of application of single-atom catalysis to chemical transformations at high temperatures.

Epidemiological analysis of pneumococcal strains isolated at Yangon Children's Hospital in Myanmar via whole-genome sequencing-based methods.

Streptococcus pneumoniae causes over one million deaths from lower respiratory infections per annum worldwide. Although mortality is very high in Southeast Asian countries, molecular epidemiological information remains unavailable for some countries. In this study, we report, for the first time, the whole-genome sequences and genetic profiles of pneumococcal strains isolated in Myanmar. We isolated 60 streptococcal strains from 300 children with acute respiratory infection at Yangon Children's Hospital in Myanmar. We obtained whole-genome sequences and identified the species, serotypes, sequence types, antimicrobial resistance (AMR) profiles, virulence factor profiles and pangenome structure using sequencing-based analysis. Average nucleotide identity analysis indicated that 58 strains were S. pneumoniae and the other 2 strains were Streptococcus mitis. The major serotype was 19F (11 strains), followed by 6E (6B genetic variant; 7 strains) and 15 other serotypes; 5 untypable strains were also detected. Multilocus sequence typing analysis revealed 39 different sequence types, including 11 novel ones. In addition, genetic profiling indicated that AMR genes and mutations spread among pneumococcal strains in Myanmar. A minimum inhibitory concentration assay indicated that several pneumococcal strains had acquired azithromycin and tetracycline resistance, whereas no strains were found to be resistant against levofloxacin and high-dose penicillin G. Phylogenetic and pangenome analysis showed various pneumococcal lineages and that the pneumococcal strains contain a rich and mobile gene pool, providing them with the ability to adapt to selective pressures. This molecular epidemiological information can help in tracking global infection and supporting AMR control in addition to public health interventions in Myanmar.

Synthesis of catalysts with fine platinum particles supported by high-surface-area activated carbons and optimization of their catalytic activities for polymer electrolyte fuel cells.

Herein, we demonstrated that carbon-supported platinum (Pt/C) is a low-cost and high-performance electrocatalyst for polymer electrolyte fuel cells (PEFCs). The ethanol reduction method was used to prepare the Pt/C catalyst, which was realized by an effective matching of the carbon support and optimization of the Pt content for preparing a membrane electrode assembly (MEA). For this, the synthesis of Pt/C catalysts with different Pt loadings was performed on two different carbons (KB1600 and KB800) as new support materials. Analysis of the XRD pattern and TEM images showed that the Pt nanoparticles (NPs) with an average diameter of ca. 1.5 nm were uniformly dispersed on the carbon surface. To further confirm the size of the NPs, the coordination numbers of Pt derived from X-ray absorption fine structure (XAFS) data were used. These results suggest that the NP size is almost identical, irrespective of Pt loading. Nitrogen adsorption-desorption analysis indicated the presence of mesopores in each carbon. The BET surface area was found to increase with increasing Pt loading, and the value of the BET surface area was as high as 1286 m2 gcarbon -1. However, after 40 wt% Pt loading on both carbons, the BET surface area was decreased due to pore blockage by Pt NPs. The oxidation reduction reaction (ORR) activity for Pt/KB1600, Pt/KB800 and commercial Pt/C was evaluated by Koutecky-Levich (K-L) analysis, and the results showed first-order kinetics with ORR. The favourable surface properties of carbon produced Pt NPs with increased density, uniformity and small size, which led to a higher electrochemical surface area (ECSA). The ECSA value of the 35 wt% Pt/KB1600 catalyst was 155.0 m2 gpt -1 higher than that of the Pt/KB800 and commercial Pt/C (36.7 wt%) catalysts. A Higher ECSA indicates more available active sites for catalyst particles. The single cell test with MEA revealed that the cell voltage in the high current density regions depends on the BET surface area, and the durability of the 35 wt% Pt/KB1600 catalyst was superior to that of the 30 wt% Pt/KB800 and commercial Pt/C (46.2 wt%) catalysts. This suggests that an optimal ratio of Pt to Pt/KB1600 catalyst provides adequate reaction sites and mass transport, which is crucial to the PEFC's high performance.

Role of BgaA as a Pneumococcal Virulence Factor Elucidated by Molecular Evolutionary Analysis.

Streptococcus pneumoniae is a major cause of pneumonia, sepsis, and meningitis. Previously, we identified a novel virulence factor by investigating evolutionary selective pressure exerted on pneumococcal choline-binding cell surface proteins. Herein, we focus on another pneumococcal cell surface protein. Cell wall-anchoring proteins containing the LPXTG motif are conserved in Gram-positive bacteria. Our evolutionary analysis showed that among the examined genes, nanA and bgaA had high proportions of codon that were under significant negative selection. Both nanA and bgaA encode a multi-functional glycosidase that aids nutrient acquisition in a glucose-poor environment, pneumococcal adherence to host cells, and evasion from host immunity. However, several studies have shown that the role of BgaA is limited in a mouse pneumonia model, and it remains unclear if BgaA affects pneumococcal pathogenesis in a mouse sepsis model. To evaluate the distribution and pathogenicity of bgaA, we performed phylogenetic analysis and intravenous infection assay. In both Bayesian and maximum likelihood phylogenetic trees, the genetic distances between pneumococcal bgaA was small, and the cluster of pneumococcal bgaA did not contain other bacterial orthologs except for a Streptococcus gwangjuense gene. Evolutionary analysis and BgaA structure indicated BgaA active site was not allowed to change. The mouse infection assay showed that the deletion of bgaA significantly reduced host mortality. These results indicated that both nanA and bgaA encode evolutionally conserved pneumococcal virulence factors and that molecular evolutionary analysis could be a useful alternative strategy for identification of virulence factors.

Visualization and understanding of the degradation behaviors of a PEFC Pt/C cathode electrocatalyst using a multi-analysis system combining time-resolved quick XAFS, three-dimensional XAFS-CT, and same-view nano-XAFS/STEM-EDS techniques.

We developed a multi-analysis system that can measure in situ time-resolved quick XAFS (QXAFS) and in situ three-dimensional XAFS-CT spatial imaging in the same area of a cathode electrocatalyst layer in a membrane-electrode assembly (MEA) of a polymer electrolyte fuel cell (PEFC) at the BL36XU beamline of SPring-8. The multi-analysis system also achieves ex situ two-dimensional nano-XAFS/STEM-EDS same-view measurements of a sliced MEA fabricated from a given place in the XAFS-CT imaged area at high spatial resolutions under a water-vapor saturated N2 atmosphere using a same-view SiN membrane cell. In this study, we applied the combination method of time-resolved QXAFS/3D XAFS-CT/2D nano-XAFS/STEM-EDS for the first time for the visualization analysis of the anode-gas exchange (AGEX) (simulation of the start-up/shut-down of PEFC vehicles) degradation process of a PEFC MEA Pt/C cathode. The AGEX cycles bring about serious irreversible degradation of both Pt nanoparticles and carbon support due to a spike-like large voltage increase. We could visualize the three-dimensional distribution and two-dimensional depth map of the amount, oxidation state (valence), Pt2+ elution, detachment, and aggregation of Pt species and the formation of carbon voids, where the change and movement of the Pt species in the cathode catalyst layer during the AGEX cycles did not proceed exceeding the 1 µm region. It is very different from the case of an ADT (an accelerated durability test between 0.6-1.0 VRHE)-degraded MEA. We discuss the spatiotemporal behavior of the AGEX degradation process and the degradation mechanism.

Feed gas exchange (startup/shutdown) effects on Pt/C cathode electrocatalysis and surface Pt-oxide behavior in polymer electrolyte fuel cells as revealed using in situ real-time XAFS and high-resolution STEM measurements.

The synchronizing measurements of both cyclic voltammograms (CVs) and real-time quick XAFSs (QXAFSs) for Pt/C cathode electrocatalysts in a membrane electrode assembly (MEA) of polymer electrolyte fuel cells (PEFCs) treated by anode-gas exchange (AGEX) and cathode-gas exchange (CGEX) cycles (startup/shutdown conditions of FC vehicles) were performed for the first time to understand the opposite effects of the AGEX and CGEX treatments on the Pt/C performance and durability and also the contradiction between the electrochemical active surface area (ECSA) decrease and the performance increase by CGEX treatment. While the AGEX treatment decreased both the ECSA and performance of MEA Pt/C due to carbon corrosion, it was found that the CGEX treatment decreased the ECSA but increased the Pt/C performance significantly due to high-index (331) facet formation (high-resolution STEM) and hence the suppression of strongly bound Pt-oxide formation at cathode Pt nanoparticle surfaces. Transient QXAFS time-profile analysis for the MEA Pt/C also revealed a direct relationship between the electrochemical performance or durability and transient kinetics of the Pt/C cathode.

Visualization Analysis of Pt and Co Species in Degraded Pt3Co/C Electrocatalyst Layers of a Polymer Electrolyte Fuel Cell Using a Same-View Nano-XAFS/STEM-EDS Combination Technique.

In order to obtain a suitable design policy for the development of a next-generation polymer electrolyte fuel cell, we performed a visualization analysis of Pt and Co species following aging and degradation processes in membrane-electrode assembly (MEA), using a same-view. Nano-X-ray absorption fine structure (XAFS)/Scanning transmission electron microscope (STEM)-energy dispersive X-ray spectroscopy (EDS) technique that we developed to elucidate durability factors and degradation mechanisms of a MEA Pt3Co/C cathode electrocatalyst with higher activity and durability than a MEA Pt/C. In the MEA Pt3Co/C, after 5000 ADT-rec (rectangle accelerated durability test) cycles, unlike the MEA Pt/C, there was no oxidation of Pt. In contrast, Co oxidized and dissolved over a wide range of the cathode layer (∼70% of the initial Co amount). The larger the size of the cracks and pores in the MEA Pt/C and the smaller the ratio of Pt/ionomer of cracks and pores, the faster the rate of catalyst degradation. In contrast, there was no correlation between the size or Co/ionomer ratio of the cracks and pores and the Co dissolution of the MEA Pt3Co/C. It was shown that Co dissolved in the electrolyte region had an octahedral Co2+-O6 structure, based on a 150 nm × 150 nm nano-XAFS analysis. It was also shown that its existence suppressed the oxidation and dissolution of Pt. The MEA Pt3Co/C after 10,000 ADT-rec cycles had many cracks and pores in the cathode electrocatalyst layer, and about 90% of Co had been dissolved and removed from the cathode layer. We discovered a metallic Pt-Co alloy band in the electrolyte region of 300-400 nm from the cathode edge and square planar Pt2+-O4 species and octahedral Co2+-O6 species in the area between the cathode edge and the Pt-Co band. The transition of Pt and Co chemical species in the Pt3Co/C cathode electrocatalyst in the MEA during the degradation process, as well as a fuel cell deterioration suppression process by Co were visualized for the first time at the nano scale using the same-view nano-XAFS/STEM-EDS combination technique that can measure the MEA under a humid N2 atmosphere while maintaining the working environment for a fuel cell.