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Abstract Single-atom catalysts (SACs) offer efficient metal utilization and distinct reactivity compared to supported metal nanoparticles. Structure-function relationships for SACs often assume that active sites have uniform coordination environments at particular binding sites on support surfaces. Here, we investigate the distribution of coordination environments of Pt SAs dispersed on shape-controlled anatase TiO2 supports specifically exposing (001) and (101) surfaces. Pt SAs on (101) are found on the surface, consistent with existing structural models, whereas those on (001) are beneath the surface after calcination. Pt SAs under (001) surfaces exhibit lower reactivity for CO oxidation than those on (101) surfaces due to their limited accessibility to gas phase species. Pt SAs deposited on commercial-TiO2 are found both at the surface and in the bulk, posing challenges to structure-function relationship development. This study highlights heterogeneity in SA coordination environments on oxide supports, emphasizing a previously overlooked consideration in the design of SACs.

Electrodeposited amorphous hydrated iridium oxide (IrOx) is a promising material for pH sensing due to its high sensitivity and the ease of fabrication. However, durability and variability continue to restrict the sensor’s effectiveness. Variation in probe films can be seen in both performance and fabrication, but it has been found that performance variation can be controlled with potentiostatic conditioning (PC). To make proper use of this technique, the morphological and chemical changes affecting the conditioning process must be understood. Here, a thorough study of this material, after undergoing PC in a pH-sensing-relevant potential regime, was conducted by voltammetry, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Fitting of XPS data was performed, guided by raw trends in survey scans, core orbitals, and valence spectra, both XPS and UPS. The findings indicate that the PC process can repeatably control and conform performance and surface bonding to desired calibrations and distributions, respectively; PC was able to reduce sensitivity and offset ranges to as low as ±0.7 mV/pH and ±0.008 V, respectively, and repeat bonding distributions over ~2 months of sample preparation. Both Ir/O atomic ratios (shifting from 4:1 to over 4.5:1) and fitted components assigned hydroxide or oxide states based on the literature (low-voltage spectra being almost entirely with suggested hydroxide components, and high-voltage spectra almost entirely with suggested oxide components) trend across the polarization range. Self-consistent valence, core orbital, and survey quantitative trends point to a likely mechanism of ligand conversion from hydroxide to oxide, suggesting that the conditioning process enforces specific state mixtures that include both theoretical Ir(III) and Ir(IV) species, and raising the conditioning potential alters the surface species from an assumed mixture of Ir species to more oxidized Ir species.

Abstract Vaccination against an airborne pathogen is very effective if it induces also the development of mucosal antibodies that can protect against infection. The mRNA‐based vaccine‐encoding SARS‐CoV‐2 full‐length spike protein (BNT162b2, Pfizer/BioNTech) protects also against infection despite being administered systemically. Here, we show that upon vaccination, cognate IgG molecules are also found in the saliva and are more abundant in SARS‐CoV‐2 previously exposed subjects, paralleling the development of plasma IgG. The antibodies titer declines at 3 months from vaccination. We identified a concentration of specific IgG in the plasma above which the relevant IgG can be detected in the saliva. Regarding IgA antibodies, we found only protease‐susceptible IgA1 antibodies in plasma while they were present at very low levels in the saliva over the course of vaccination of SARS‐CoV‐2‐naïve subjects. Thus, in response to BNT162b2 vaccine, plasma IgG can permeate into mucosal sites and participate in viral protection. It is not clear why IgA1 are detected in low amount, they may be proteolytically cleaved.

OBJECTIVES The prevalence of diabetes mellitus is rapidly increasing in Vietnam, particularly among adults aged over 45 years. This study estimated trends in diabetes and prediabetes prevalence and determined risk factors in Vietnamese adults (over 45 years). METHODS A cross-sectional study was conducted based on data from an annual diabetes screening program among people aged 45-69 years in an urban city in central Vietnam (Da Nang). Joinpoint regression analyses were performed to calculate the annual percentage change and ptrend-values. Multinomial logistic regression analysis was used to determine risk factors. RESULTS In total, 3,765 men and 9,149 women were included in this analysis. The age-adjusted prevalence of diabetes and prediabetes in 2017 was 11.4% and 52.9%, respectively. The prevalence of diabetes was higher in men (15.1%) than in women (10.3%), but that of prediabetes was similar in both genders (53.4% vs. 52.8%). The prevalence of prediabetes significantly increased during the study period, whereas no upward or downward trend for diabetes was observed. The prevalence of obesity, abdominal obesity, hypertension, and dyslipidemia showed no obvious trend. Obesity, a high waist-to-hip ratio, hypertension, more severe abdominal obesity, and dyslipidemia were significantly associated with a higher risk of diabetes and prediabetes. CONCLUSIONS Diabetes and prediabetes were more prevalent among people aged over 45 years than in the general population. Da Nang has experienced a marked increase in the prevalence of prediabetes. These findings have significant implications regarding the need for nationwide public health interventions and management aiming at diabetes prevention and control.

Single-atom catalysts (SACs) offer efficient metal utilization and distinct reactivity compared to supported metal nanoparticles. Structure-function relationships for SACs often assume that active sites have uniform coordination environments at particular binding sites on support surfaces. Here, we investigate the distribution of coordination environments of Pt SAs dispersed on shape-controlled anatase TiO2 supports specifically exposing (001) and (101) surfaces. Pt SAs on (101) are found on the surface, consistent with existing structural models, whereas those on (001) are beneath the surface after calcination. Pt SAs under (001) surfaces exhibit lower reactivity for CO oxidation than those on (101) surfaces due to their limited accessibility to gas phase species. Pt SAs deposited on commercial-TiO2 are found both at the surface and in the bulk, posing challenges to structure-function relationship development. This study highlights heterogeneity in SA coordination environments on oxide supports, emphasizing a previously overlooked consideration in the design of SACs.

Electrodeposited amorphous hydrated iridium oxide (IrOx) is a promising material for pH sensing due to its high sensitivity and the ease of fabrication. However, durability and variability continue to restrict the sensors effectiveness. Variation in probe films can be seen in both performance and fabrication, but it has been found that performance variation can be controlled with potentiostatic conditioning (PC). To make proper use of this technique, the morphological and chemical changes affecting the conditioning process must be understood. Here, a thorough study of this material, after undergoing PC in a pH-sensing-relevant potential regime, was conducted by voltammetry, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Fitting of XPS data was performed, guided by raw trends in survey scans, core orbitals, and valence spectra, both XPS and UPS. The findings indicate that the PC process can repeatably control and conform performance and surface bonding to desired calibrations and distributions, respectively; PC was able to reduce sensitivity and offset ranges to as low as ±0.7 mV/pH and ±0.008 V, respectively, and repeat bonding distributions over ~2 months of sample preparation. Both Ir/O atomic ratios (shifting from 4:1 to over 4.5:1) and fitted components assigned hydroxide or oxide states based on the literature (low-voltage spectra being almost entirely with suggested hydroxide components, and high-voltage spectra almost entirely with suggested oxide components) trend across the polarization range. Self-consistent valence, core orbital, and survey quantitative trends point to a likely mechanism of ligand conversion from hydroxide to oxide, suggesting that the conditioning process enforces specific state mixtures that include both theoretical Ir(III) and Ir(IV) species, and raising the conditioning potential alters the surface species from an assumed mixture of Ir species to more oxidized Ir species.

Catalytic substrate, which is devoid of expensive noble metals and enzymes for hydrogen peroxide (H2O2), reduction reactions can be obtained via nitrogen doping of graphite. Here, we report a facile fabrication method for obtaining such nitrogen doped graphitized carbon using polyacrylonitrile (PAN) mats and its use in H2O2 sensing. A high degree of graphitization was obtained with a mechanical treatment of the PAN fibers embedded with carbon nanotubes (CNT) prior to the pyrolysis step. The electrochemical testing showed a limit of detection (LOD) 0.609 µM and sensitivity of 2.54 µA cm−2 mM−1. The promising sensing performance of the developed carbon electrodes can be attributed to the presence of high content of pyridinic and graphitic nitrogens in the pyrolytic carbons, as confirmed by X-ray photoelectron spectroscopy. The reported results suggest that, despite their simple fabrication, the hydrogen peroxide sensors developed from pyrolytic carbon nanofibers are comparable with their sophisticated nitrogen-doped graphene counterparts.

We have characterized soot particles measured in situ in a laminar co-flow ethylene-air diffusion flame using small-angle X-ray scattering (SAXS). The analysis includes temperature measurements made with coherent anti-Stokes Raman spectroscopy (CARS) and complements soot volume-fraction and maturity measurements made with laser-induced incandescence (LII). We compared the results of fits to the SAXS measurements using a unified model and a fractal core-shell model. Power-law parameters yielded by the unified model indicate that aggregates of primary particles are in the mass-fractal regime, whereas the primary particles are in the surface-fractal regime in the middle of the flame. Higher and lower in the flame, the primary-particle power-law parameter approaches 4, suggesting smooth primary particles. These trends are consistent with fits using the fractal core-shell model, which indicate that particles have an established core-shell structure in the middle of the flame and are internally homogeneous at higher and lower heights in the flame. Primary-particle size distributions derived using the fractal core-shell model demonstrate excellent agreement with distributions inferred from transmission electron microscopy (TEM) images in the middle of the flame. Higher in the flame, a second small mode appears in the size distributions, suggesting particle fragmentation during oxidation. Surface oxidation would explain (1) aggregate fragmentation and (2) loss of core-shell structure leading to smoother primary-particle surfaces by removal of carbon overlayers. SAXS measurements are much more sensitive to incipient and young soot particles than LII and demonstrate significant volume fraction from particles low in the flame where the LII signal is negligible.

We have developed a strategy for distinguishing between small-angle X-ray scattering (SAXS) from gas-phase species and newly formed nanoparticles in mixed gas- and particle-phase reacting flows. This methodology explicitly accounts for temperature-dependent scattering from gases. We measured SAXS in situ in a sooting linear laminar partially premixed co-flow ethylene/air diffusion flame. The scattering signal demonstrates a downward curvature as a function of the momentum transfer (q) at q values of 0.2-0.57 Å-1. The q-dependent curvature is consistent with the Debye equation and the independent-atom model for gas-phase scattering. This behavior can also be modeled using the Guinier approximation and could be characterized as a Guinier knee for gas-phase scattering. The Guinier functional form can be fit to the scattering signal in this q range without a priori knowledge of the gas-phase composition, enabling estimation of the gas-phase contribution to the scattering signal while accounting for changes in the gas-phase composition and temperature. We coupled the SAXS measurements with in situ temperature measurements using coherent anti-Stokes Raman spectroscopy. This approach to characterizing the gas-phase SAXS signal provides a physical basis for distinguishing among the contributions to the scattering signal from the instrument function, flame gases, and nanoparticles. The results are particularly important for the analysis of the SAXS signal in the q range associated with particles in the size range of 1-6 nm.

Catalytic substrate, which is devoid of expensive noble metals and enzymes for hydrogen peroxide (H₂O₂), reduction reactions can be obtained via nitrogen doping of graphite. Here, we report a facile fabrication method for obtaining such nitrogen doped graphitized carbon using polyacrylonitrile (PAN) mats and its use in H₂O₂ sensing. A high degree of graphitization was obtained with a mechanical treatment of the PAN fibers embedded with carbon nanotubes (CNT) prior to the pyrolysis step. The electrochemical testing showed a limit of detection (LOD) 0.609 µM and sensitivity of 2.54 µA cm-2 mM-1. The promising sensing performance of the developed carbon electrodes can be attributed to the presence of high content of pyridinic and graphitic nitrogens in the pyrolytic carbons, as confirmed by X-ray photoelectron spectroscopy. The reported results suggest that, despite their simple fabrication, the hydrogen peroxide sensors developed from pyrolytic carbon nanofibers are comparable with their sophisticated nitrogen-doped graphene counterparts.