Sub-nanometric High-Entropy Alloy Cluster: Hydrogen Spillover Driven Synthesis on CeO2 and Structural Reversibility.

High-entropy alloy (HEA) nanoparticles (NPs) have attracted significant attention as promising catalysts owing to the various unique synergistic effects originating from the nanometer-scale, near-equimolar mixing of five or more components to produce single-phase solid solutions. However, the study of sub-nanometer HEA clusters having sizes of less than 1 nm remains incomplete despite the possibility of novel functions related to borderline molecular states with discrete quantum energy levels. The present work demonstrates the synthesis of CeO2 nanorods (CeO2-NRs) on which sub-nanometer CoNiCuZnPd HEA clusters were formed with the aid of a pronounced hydrogen spillover effect on readily reducible CeO2 (110) facets. The CoNiCuZnPd HEA sub-nanoclusters exhibited higher activity during the reduction of NO by H2 even at low temperatures compared with the corresponding monometallic catalysts. These clusters also showed a unique structural reversibility in response to repeated exposure to oxidative/reductive conditions, based on the sacrificial oxidation of the non-noble metals. Both experimental and theoretical analyses established that multielement mixing in quantum-sized regions endowed the HEA clusters with entirely novel catalytic properties.

Nomograms predicting extra- and early intrahepatic recurrence after hepatic resection of hepatocellular carcinoma.

BACKGROUND: Extrahepatic recurrence and early intrahepatic recurrence of hepatocellular carcinoma after hepatic resection are indicative of poor prognoses. We aimed to develop nomograms to predict extrahepatic recurrence and early intrahepatic recurrence after hepatic resection. METHODS: The participants of this study were 1,206 patients who underwent initial and curative hepatic resection for hepatocellular carcinoma. Multivariate logistic regression analyses using the Akaike information criterion were used to construct nomograms to predict extrahepatic recurrence and early intrahepatic recurrence (within 1 year of surgery) at the first recurrence sites after hepatic resection. Performance of each nomogram was evaluated by calibration plots with bootstrapping. RESULTS: Extrahepatic recurrence was identified in 95 patients (7.9%) and early intrahepatic recurrence in 296 patients (24.5%). Three predictive factors, α-fetoprotein >200 ng/mL, tumor size (3-5 cm or >5 cm vs ≤3 cm), and image-diagnosed venous invasion by computed tomography, were adopted in the final model of the extrahepatic recurrence nomogram with a concordance index of 0.75. Tumor size and 2 additional predictors (ie, multiple tumors and image-diagnosed portal invasion) were adopted in the final model of the early intrahepatic recurrence nomogram with a concordance index of 0.67. The calibration plots showed good agreement between the nomogram predictions of extrahepatic recurrence and early intrahepatic recurrence and the actual observations of extrahepatic recurrence and early intrahepatic recurrence, respectively. CONCLUSION: We have developed reliable nomograms to predict extrahepatic recurrence and early intrahepatic recurrence of hepatocellular carcinoma after hepatic resection. These are useful for the diagnostic prediction of extrahepatic recurrence and early intrahepatic recurrence and could guide the surgeon's selection of treatment strategies for hepatocellular carcinoma patients.