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Background: We previously demonstrated the validity of a regression model that included ethnicity as a novel predictor for predicting normative brain volumes in old age. The model was optimized using brain volumes measured with a standard tool FreeSurfer. Objective: Here we further verified the prediction model using newly estimated brain volumes from Neuro I, a quantitative brain analysis system developed for Korean populations. Methods: Lobar and subcortical volumes were estimated from MRI images of 1,629 normal Korean and 786 Caucasian subjects (age range 59–89) and were predicted in linear regression from ethnicity, age, sex, intracranial volume, magnetic field strength, and scanner manufacturers. Results: In the regression model predicting the new volumes, ethnicity was again a substantial predictor in most regions. Additionally, the model-based z-scores of regions were calculated for 428 AD patients and the matched controls, and then employed for diagnostic classification. When the AD classifier adopted the z-scores adjusted for ethnicity, the diagnostic accuracy has noticeably improved (AUC = 0.85, ΔAUC = + 0.04, D = 4.10, p < 0.001). Conclusions: Our results suggest that the prediction model remains robust across different measurement tool, and ethnicity significantly contributes to the establishment of norms for brain volumes and the development of a diagnostic system for neurodegenerative diseases. [ABSTRACT FROM AUTHOR]

Electron beams are versatile tools for nanoscale fabrication processes, however, the underlying e-beam chemistry remains in its infancy. Through operando transmission electron microscopy investigations, we elucidate a redox-driven cargo release of individual metal atoms triggered by electron beams. The chosen organic delivery molecule, tetraphenylporphyrin (TPP), proves highly versatile, forming complexes with nearly all metals from the periodic table and being easily processed in solution. A comprehensive cinematographic analysis of the dynamics of single metal atoms confirms the nearly instantaneous ejection of complexed metal atoms under an 80 kV electron beam, underscoring the system's broad versatility. Providing mechanistic insights, we employ density functional theory to support the proposed reductive demetallation pathway facilitated by secondary electrons, contributing novel perspectives to electron beam-mediated chemical reaction mechanisms. Lastly, our findings demonstrate that all seven metals investigated form nanoclusters once ejected from TPP, highlighting the method's potential for studying and developing sustainable single-atom and nanocluster catalysts. [ABSTRACT FROM AUTHOR]

Dedications to achieve the highly efficient metal oxide semiconductor for the photoelectrochemical water splitting system have been persisted to utilize the TiO2 as the promising photoanode material. Herein, we report notable progress for nanostructured TiO2 photoanodes using facile sequential one-pot hydrothermal synthesis and annealing in hydrogen. A photocurrent density of 3.04 mA·cm−2 at 1.23 V vs. reversible hydrogen electrode was achieved in TiO2 nanorod arrays annealed in hydrogen ambient, which is approximately 4.25 times higher than that of pristine TiO2 annealed in ambient air. 79.2% of incident photon-to-current efficiency at 380 nm wavelength demonstrates the prominence of the material at the near-UV spectral range region and 100 h chronoamperometric test exhibits the stability of the photoanode. Detailed studies regarding crystallinity, bandgap, and elemental analysis provide the importance of the optimized annealing condition for the TiO2-based photoanodes. Water contact angle measurement displays the effect of hydrogen annealing on the hydrophilicity of the material. This study clearly demonstrates the marked improvement using the optimized hydrogen annealing, providing the promising methodologies for eco-friendly mass production of water splitting photoelectrodes. [ABSTRACT FROM AUTHOR]

Highlights: Two types of BiVO4/TiO2 heterostructure photoanodes comprising TiO2 nanorods (NRs) and TiO2 nanoflowers (NFs) with different (001) and (110) crystal facets, respectively, were designed. The higher photoactivity of BiVO4/TiO2 NFs than BiVO4/TiO2 NRs was attributed to the improvement of charge separation by the TiO2 NFs. The formation of type II band alignment between BiVO4 nanodots and TiO2 NFs expedited electron transport and reduced charge recombination.Although bismuth vanadate (BiVO4) has been promising as photoanode material for photoelectrochemical water splitting, its charge recombination issue by short charge diffusion length has led to various studies about heterostructure photoanodes. As a hole blocking layer of BiVO4, titanium dioxide (TiO2) has been considered unsuitable because of its relatively positive valence band edge and low electrical conductivity. Herein, a crystal facet engineering of TiO2 nanostructures is proposed to control band structures for the hole blocking layer of BiVO4 nanodots. We design two types of TiO2 nanostructures, which are nanorods (NRs) and nanoflowers (NFs) with different (001) and (110) crystal facets, respectively, and fabricate BiVO4/TiO2 heterostructure photoanodes. The BiVO4/TiO2 NFs showed 4.8 times higher photocurrent density than the BiVO4/TiO2 NRs. Transient decay time analysis and time-resolved photoluminescence reveal the enhancement is attributed to the reduced charge recombination, which is originated from the formation of type II band alignment between BiVO4 nanodots and TiO2 NFs. This work provides not only new insights into the interplay between crystal facets and band structures but also important steps for the design of highly efficient photoelectrodes. [ABSTRACT FROM AUTHOR]

The rising prospects of mechanochemically assisted syntheses hold promise for both academia and industry, yet they face challenges in understanding and, therefore, anticipating respective reaction kinetics. Particularly, dependencies based on variations in milling equipment remain little understood and globally overlooked. This study aims to address this issue by identifying critical parameters through kinematic models, facilitating the reproducibility of mechanochemical reactions across the most prominent mills in laboratory settings, namely planetary and mixer mills. Through a series of selected experiments replicating major classes of organic, organometallic, transition metal‐catalyzed, and inorganic reactions from literature, we rationalize the independence of kinematic parameters on reaction kinetics when the accumulated energy criterion is met. As a step forward and to facilitate the practicability of our findings, we provide a freely accessible online tool[†] that allows the calculation of respective energy parameters for different planetary and mixer mills. Our work advances the current understanding of mechanochemistry and lays the foundation for future rational exploration in this rapidly evolving field. [ABSTRACT FROM AUTHOR]

CuO-added (Li xK0.9− x Na0.1)NbO3 [C(L xK0.9− x N0.1)N] ceramics with 0.0≤ x≤0.05 were well-sintered at 960°C for 6 hours. The lattice parameters of the specimens decreased with the addition of Li2O. Defect polarization ( PD) formed between Cu2+ions and oxygen vacancies. Double polarization vs electric field ( P-E) hysteresis and sprout-shaped strain vs electric field ( S-E) curves were observed in these specimens with a large strain of 0.16% at 7.0 kV/mm, possibly owing to the presence of PD. When the P-E curve was measured at temperatures higher than 75°C, the C(K0.9N0.1)N ceramic exhibited a normal P-E hysteresis curve, whereas the C(L0.04K0.86N0.1)N ceramic maintained the double P-E hysteresis curve up to 125°C, indicating that Li2O increased the thermal stability of PD. The latter specimen also showed the sprout shaped S-E curve with a strain of 0.15% at 7.0 kV/mm after 104 cycles of a high electric field of 7.0 kV/mm. [ABSTRACT FROM AUTHOR]

CuO-added (1- x) KNbO3- x mol%BaZrO3 ceramics with 0.0≤ x≤7.0 were sintered at 960°C. Large double polarization vs electric field ( P-E) and sprout-shaped strain vs electric field ( S-E) hysteresis curves were obtained from the specimens with x≤2.0. They exhibited large polarizing electric fields ( EP) owing to the presence of a large number of defect dipoles ( PDs) that formed between Cu2+ ions and oxygen vacancies. Small double P-E hysteresis curves were observed for the specimens with x≥3.0 with reduced EP because of the decreased number of PDs and the presence of a polymorphic phase structure containing both orthorhombic and pseudocubic structures. In particular, the specimen with x=5.0 exhibited a large strain of 0.16% at 8.0 kV/mm with a small EP of 1.2 kV/mm and good fatigue property: this specimen maintained a strain of 0.13% at 6.0 kV/mm after 106 cycles of 3.0 kV/mm. [ABSTRACT FROM AUTHOR]

A specimen having a stoichiometric composition of KSbO3·(KSb) calcined at 800°C has an R3 rhombohedral structure (RS), and changes to a Pn3 cubic structure (CS) when calcined at 1100°C. Finally, a <111>-oriented rhombohedral phase is formed in the specimen calcined at 1230°C. K/Sb ratio decreases from 1.0 in RS, 0.93 in CS, and finally to 0.85 in <111>-oriented rhombohedral phases. On the other hand, a specimen having a K-excess composition of K1.1SbO3 calcined at 800°C shows a RS that is maintained in the K-excess specimen calcined at 1230°C. The composition of these specimens is very close to KSb. Therefore, the RS with a space group of R3 is a stable form of KSbO3. The formation of Pn3 cubic and <111>-oriented R3 phases can be explained by the evaporation of K2O during the calcination process at temperatures above 1100°C. [ABSTRACT FROM AUTHOR]

Background: We previously demonstrated the validity of a regression model that included ethnicity as a novel predictor for predicting normative brain volumes in old age. The model was optimized using brain volumes measured with a standard tool FreeSurfer. Objective: Here we further verified the prediction model using newly estimated brain volumes from Neuro I, a quantitative brain analysis system developed for Korean populations. Methods: Lobar and subcortical volumes were estimated from MRI images of 1,629 normal Korean and 786 Caucasian subjects (age range 59–89) and were predicted in linear regression from ethnicity, age, sex, intracranial volume, magnetic field strength, and scanner manufacturers. Results: In the regression model predicting the new volumes, ethnicity was again a substantial predictor in most regions. Additionally, the model-based z-scores of regions were calculated for 428 AD patients and the matched controls, and then employed for diagnostic classification. When the AD classifier adopted the z-scores adjusted for ethnicity, the diagnostic accuracy has noticeably improved (AUC = 0.85, ΔAUC = + 0.04, D = 4.10, p < 0.001). Conclusions: Our results suggest that the prediction model remains robust across different measurement tool, and ethnicity significantly contributes to the establishment of norms for brain volumes and the development of a diagnostic system for neurodegenerative diseases. [ABSTRACT FROM AUTHOR]