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.

Subnanometric Osmium Clusters Confined on Palladium Metallenes for Enhanced Hydrogen Evolution and Oxygen Reduction Catalysis.

Highly efficient, cost-effective, and durable electrocatalysts, capable of accelerating sluggish reaction kinetics and attaining high performance, are essential for developing sustainable energy technologies but remain a great challenge. Here, we leverage a facile heterostructure design strategy to construct atomically thin Os@Pd metallenes, with atomic-scale Os nanoclusters of varying geometries confined on the surface layer of the Pd lattice, which exhibit excellent bifunctional properties for catalyzing both hydrogen evolution (HER) and oxygen reduction reactions (ORR). Importantly, Os5%@Pd metallenes manifest a low η10 overpotential of only 11 mV in 1.0 M KOH electrolyte (HER) as well as a highly positive E1/2 potential of 0.92 V in 0.1 M KOH (ORR), along with superior mass activities and electrochemical durability. Theoretical investigations reveal that the strong electron redistribution between Os and Pd elements renders a precise fine-tuning of respective d-band centers, thereby guiding adsorption of hydrogen and oxygen intermediates with an appropriate binding energy for the optimal HER and ORR.

Preparation of Jellyfish Mucin.

A mucin-type glycoprotein extracted from various species of jellyfish (JF) is named qniumucin (Q-mucin). Compared with general mucins, most of which are from mammals including humans, Q-mucin can be collected on a relatively large scale with high yield. Owing to its simple structure with low heterogeneity, Q-mucin has a potential to be developed into material mucins which opens various applications valuable to humans. On the basis of our present knowledge, here, we describe our protocol for the extraction of Q-mucin, which can be extracted from any JF species worldwide. Experimental protocols to identify the structure of Q-mucin are also introduced.

Pd-PdO Nanodomains on Amorphous Ru Metallene Oxide for High-Performance Multifunctional Electrocatalysis.

Developing highly efficient multifunctional electrocatalysts is crucial for future sustainable energy  pursuits, but remains a great challenge. Herein, a facile synthetic strategy is used to confine atomically thin Pd-PdO nanodomains to amorphous Ru metallene oxide (RuO2 ). The as-synthesized electrocatalyst (Pd2 RuOx-0.5 h) exhibits excellent catalytic activity toward the pH-universal hydrogen evolution reaction (η10  = 14 mV in 1 m KOH, η10  = 12 mV in 0.5 m H2 SO4 , and η10  = 22 mV in 1 m PBS), alkaline oxygen evolution reaction (η10  = 225 mV), and overall water splitting (E10  = 1.49 V) with high mass activity and operational stability. Further reduction endows the material (Pd2 RuOx-2 h) with a promising alkaline oxygen reduction activity, evidenced by high halfway potential, four-electron selectivity, and excellent poison tolerance. The enhanced catalytic activity is attributed to the rational integration of favorable nanostructures, including 1) the atomically thin nanosheet morphology, 2) the coexisting amorphous and defective crystalline phases, and 3) the multi-component heterostructural features. These structural factors effectively regulate the material's electronic configuration and the adsorption of intermediates at the active sites for favorable reaction energetics.

Jellyfish mucin (qniumucin) extracted with a modified protocol indicated its existence as a constituent of the extracellular matrix.

Jellyfish (JF) mucin (precisely, a mucin-type glycoprotein named qniumucin: Q-mucin) first discovered in JF is mainly composed of highly O-glycosylated domains, and its unique structure suggests its wide applications as a smart material. In this study, the standard protocol used to date was thoroughly reinvestigated because the processing of raw JF was rather difficult and continuous production from frozen sources was also indispensable. Finally, we concluded that Q-mucin is involved not in mucus but in the mesoglea, i.e., the extracellular matrix (ECM), as a part of a very large polymer complex. We added a treatment procedure with a chelate reagent (e.g. EDTA) to inactivate endogenous proteases that induce the spontaneous decomposition of the collagens in ECM. The amino acid composition (AAC) of each precipitate formed upon EtOH addition indicated that Q-mucin dissociates from the biopolymer complex as a constituent highly soluble in deionized water. Since the remaining portion of ECM still seemed to contain a large amount of the precursor of Q-mucin even after the extraction with water is completed, the yield of Q-mucin is expected to increase markedly if an innovative method to decompose EtOH precipitates is developed. The existence of Q-mucin in ECM seems to be described in parallel with that of proteoglycans (PG) in mammalian cartilage because they resemble each other.

Intraductal tubulopapillary neoplasm (ITPN) of the pancreas: a distinct entity among pancreatic tumors.

AIMS: Intraductal tubulopapillary neoplasm (ITPN) of the pancreas is a recently recognized pancreatic tumor entity. Here we aimed to determine the most important features with a systematic review coupled with an integrated statistical approach. METHODS AND RESULTS: PubMed, SCOPUS, and Embase were searched for studies reporting data on pancreatic ITPN. The clinicopathological, immunohistochemical, and molecular data were summarized. Then a comprehensive survival analysis and a comparative analysis of the molecular alterations of ITPN with those of pancreatic ductal adenocarcinoma (PDAC) and intraductal papillary mucinous neoplasm (IPMN) from reference cohorts (including the International Cancer Genome Consortium- ICGC dataset and The Cancer Genome Atlas, TCGA program) were conducted. The core findings of 128 patients were as follows: (i) Clinicopathological parameters: pancreatic head is the most common site; presence of an associated adenocarcinoma was reported in 60% of cases, but with rare nodal metastasis. (ii) Immunohistochemistry: MUC1 (>90%) and MUC6 (70%) were the most frequently expressed mucins. ITPN lacked the intestinal marker MUC2; unlike IPMN, it did not express MUC5AC. (iii) Molecular landscape: Compared with PDAC/IPMN, the classic pancreatic drivers KRAS, TP53, CDKN2A, SMAD4, GNAS, and RNF43 were less altered in ITPN (P < 0.001), whereas MCL amplifications, FGFR2 fusions, and PI3KCA mutations were commonly altered (P < 0.001). (iv) Survival analysis: ITPN with a "pure" branch duct involvement showed the lowest risk of recurrence. CONCLUSION: ITPN is a distinct pancreatic neoplasm with specific clinicopathological and molecular characteristics. Its recognition is fundamental for its clinical/prognostic implications and for the enrichment of potential targets for precision oncology.

Nontraditional Aldol Condensation Performance of Highly Efficient and Reusable Cs+ Single Sites in ß-Zeolite Channels.

Aldol reactions (self- and cross-aldol condensations) for conjugated enone synthesis were efficiently performed on large-sized Cs+ single sites (1 wt %) confined in ß-zeolite channels in toluene, which showed the highest level of catalytic aldol condensation activity among reported zeolite catalysts. In general, aldol condensation reactions for C-C bond synthesis can proceed by acids (e.g., H+), bases (e.g., OH-), enolate species, and acidic or basic solid catalysts. However, the Cs+ single site/ß sample without significant acid-base property showed unprecedented, efficient, and reusable catalysis for self-aldol and cross-aldol condensations. Intrinsically inactive Cs+ single sites due to the noble-gas electronic structure were transformed to active Cs+ single sites in ß-zeolite channels. Cs+/ß has many advantages such as broad substrate scope, eco-friendliness, high product selectivity and yield, and simple work-up procedure. Thus, the Cs+ single site/ß provides an attractive and useful methodology for practical C-C bond synthesis. On the basis of the Cs+/ß characterization by X-ray photoelectron spectroscopy (XPS), in situ X-ray absorption fine structure (XAFS) (X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS)), and temperature-programmed desorption (TPD), density functional theory (DFT) calculations of the self- and cross-aldol condensation reaction pathways involving the transition states on the Cs+ single site in ß-zeolite channel revealed nontraditional concerted interligand bond rearrangement mechanisms.

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.

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.

Robust and Stable Acidic Overall Water Splitting on Ir Single Atoms.

Single-atom electrocatalysts (SAEs) can realize the target of low-cost by maximum atomic efficiency. However, they usually suffer performance decay due to high energy states, especially in a harsh acidic water splitting environment. Here, we conceive and realize a double protecting strategy that ensures robust acidic water splitting on Ir SAEs by dispersing Ir atoms in/onto Fe nanoparticles and embedding IrFe nanoparticles into nitrogen-doped carbon nanotubes (Ir-SA@Fe@NCNT). When Ir-SA@Fe@NCNT acts as a bifunctional electrocatalyst at ultralow Ir loading of 1.14 µg cm-2, the required overpotentials to deliver 10 mA cm-2 are 250 and 26 mV for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in 0.5 M H2SO4 electrolyte corresponding to 1370- and 61-fold better mass activities than benchmark IrO2 and Pt/C at an overpotential of 270 mV, respectively, resulting in only 1.51 V to drive overall water splitting. Moreover, remarkable stability is also observed compared to Pt/C-IrO2.

Secondary-Atom-Doping Enables Robust Fe-N-C Single-Atom Catalysts with Enhanced Oxygen Reduction Reaction.

Single-atom catalysts (SACs) with nitrogen-coordinated nonprecious metal sites have exhibited inimitable advantages in electrocatalysis. However, a large room for improving their activity and durability remains. Herein, we construct atomically dispersed Fe sites in N-doped carbon supports by secondary-atom-doped strategy. Upon the secondary doping, the density and coordination environment of active sites can be efficiently tuned, enabling the simultaneous improvement in the number and reactivity of the active site. Besides, structure optimizations in terms of the enlarged surface area and improved hydrophilicity can be achieved simultaneously. Due to the beneficial microstructure and abundant highly active FeN5 moieties resulting from the secondary doping, the resultant catalyst exhibits an admirable half-wave potential of 0.81 V versus 0.83 V for Pt/C and much better stability than Pt/C in acidic media. This work would offer a general strategy for the design and preparation of highly active SACs for electrochemical energy devices.

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.

NH3 -Driven Benzene C-H Activation with O2 that Opens a New Way for Selective Phenol Synthesis.

Catalytic benzene C-H activation toward selective phenol synthesis with O2 remains a stimulating challenge to be tackled. Phenol is currently produced industrially by the three-steps cumene process in liquid phase, which is energy-intensive and not environmentally friendly. Hence, there is a strong demand for an alternative gas-phase single-path reaction process. This account documents the pivotal confined single metal ion site platform with a sufficiently large coordination sphere in ß zeolite pores, which promotes the unprecedented catalysis for the selective benzene hydroxylation with O2 under coexisting NH3 by the new inter-ligand concerted mechanism. Among alkali and alkaline-earth metal ions and transition and precious metal ions, single Cs+ and Rb+ sites with ion diameters >0.300 nm in the ß pores exhibited good performances for the direct phenol synthesis in a gas-phase single-path reaction process. The single Cs+ and Rb+ sites that possess neither significant Lewis acidic-basic property nor redox property, cannot activate benzene, O2 , and NH3 , respectively, whereas when they coadsorbed together, the reaction of the inter-coadsorbates on the single alkali-metal ion site proceeds concertedly (the inter-ligand concerted mechanism), bringing about the benzene C-H activation toward phenol synthesis. The NH3 -driven benzene C-H activation with O2 was compared to the switchover of the reaction pathways from the deep oxidation to selective oxidation of benzene by coexisting NH3 on Pt6 metallic cluster/ß and Ni4 O4 oxide cluster/ß. The NH3 -driven selective oxidation mechanism observed with the Cs+ /ß and Rb+ /ß differs from the traditional redox catalysis (Mars-van Krevelen) mechanism, simple Langmuir-Hinshelwood mechanism, and acid-base catalysis mechanism involving clearly defined interaction modes. The present catalysis concept opens a new way for catalytic selective oxidation processes involving direct phenol synthesis.

An Integrated Single-Electrode Method Reveals the Template Roles of Atomic Steps: Disturb Interfacial Water Networks and Thus Affect the Reactivity of Electrocatalysts.

A method enabling the accurate and precise correlation between structures and properties is critical to the development of efficient electrocatalysts. To this end, we developed an integrated single-electrode method (ISM) that intimately couples electrochemical rotating disk electrodes, in situ/operando X-ray absorption fine structures, and aberration-corrected transmission electron microscopy on identical electrodes. This all-in-one method allows for the one-to-one, in situ/operando, and atomic-scale correlation between structures of electrocatalysts with their electrochemical reactivities, distinct from common methods that adopt multisamples separately for electrochemical and physical characterizations. Because the atomic step is one of the most fundamentally structural elements in electrocatalysts, we demonstrated the feasibility of ISM by exploring the roles of atomic steps in the reactivity of electrocatalysts. In situ and atomic-scale evidence shows that low-coordinated atomic steps not only generate reactive species at low potentials and strengthen surface contraction but also act as templates to disturb interfacial water networks and thus affect the reactivity of electrocatalysts. This template role interprets the long-standing puzzle regarding why high-index facets are active for the oxygen reduction reaction in acidic media. The ISM as a fundamentally new method for workflows should aid the study of many other electrocatalysts regarding their nature of active sites and operative mechanisms.

Key Factors for Simultaneous Improvements of Performance and Durability of Core-Shell Pt3 Ni/Carbon Electrocatalysts Toward Superior Polymer Electrolyte Fuel Cell.

It remains a big challenge to remarkably improve both oxygen reduction reaction (ORR) activity and long-term durability of Pt-M bimetal electrocatalysts simultaneously in the harsh cathode environment toward widespread commercialization of polymer electrolyte fuel cells (PEFC). In this account we found double-promotional effects of carbon micro coil (CMC) support on ORR performance and durability of octahedral Pt3 Ni nanoparticles (Oh Pt3 Ni/CMC). The Oh Pt3 Ni/CMC displayed remarkable improvements of mass activity (MA; 13.6 and 34.1 times) and surface specific activity (SA; 31.3 and 37.0 times) compared to those of benchmark Pt/C (TEC10E20E) and Pt/C (TEC10E50E-HT), respectively. Notably, the Oh Pt3 Ni/CMC revealed a negligible MA loss after 50,000 triangular-wave 1.0-1.5 VRHE (startup/shutdown) load cycles, contrasted to MA losses of 40 % (TEC10E20E) and 21.5 % (TEC10E50E-HT) by only 10,000 load cycles. It was also found that the SA increased exponentially with the decrease in the CO stripping peak potential in a series of Pt-M/carbon (M: Ni and Co), which predicts a maximum SA at the curve asymptote. Key factors for simultaneous improvements of performance and durability of core-shell Pt3 Ni/carbon electrocatalysts toward superior PEFC is also discussed.

Observation of Degradation of Pt and Carbon Support in Polymer Electrolyte Fuel Cell Using Combined Nano-X-ray Absorption Fine Structure and Transmission Electron Microscopy Techniques.

It is hard to directly visualize spectroscopic and atomic-nanoscopic information on the degraded Pt/C cathode layer inside polymer electrolyte fuel cell (PEFC). However, it is mandatory to understand the preferential area, sequence, and relationship of the degradations of Pt nanoparticles and carbon support in the Pt/C cathode layer by directly observing the Pt/C cathode catalyst for the development of next-generation PEFC cathode catalysts. Here, the spectroscopic, chemical, and morphological visualization of the degradation of Pt/C cathode electrocatalysts in PEFC was performed successfully by a same-view combination technique of nano-X-ray absorption fine structure (XAFS) and transmission electron microscopy (TEM)/scanning TEM-energy-dispersive spectrometry (EDS) under a humid N2 atmosphere. The same-view nano-XAFS and TEM/STEM-EDS imaging of the Pt/C cathode of PEFC after triangular-wave 1.0-1.5 VRHE (startup/shutdown) accelerated durability test (tri-ADT) cycles elucidated the site-selective area, sequence, and relationship of the degradations of Pt nanoparticles and carbon support in the Pt/C cathode layer. The 10 tri-ADT cycles caused a carbon corrosion to reduce the carbon size preferentially in the boundary regions of the cathode layer with both electrolyte and holes/cracks, accompanied with detachment of Pt nanoparticles from the degraded carbon. After the decrease in the carbon size to less than 8 nm by the 20 tri-ADT cycles, Pt nanoparticles around the extremely corroded carbon areas were found to transform and dissolve into oxidized Pt2+-O4 species.

Extranodal extension of nodal metastases is a poor prognostic moderator in non-small cell lung cancer: a meta-analysis.

Extranodal extension (ENE) of nodal metastasis is defined as the extension of metastatic cells through the nodal capsule into the perinodal tissue. This morphological parameter, recently proposed as an important prognostic factor in different types of malignancy, has not been included in the TNM staging system for non-small cell lung cancer (NSCLC). In this systematic review with meta-analysis, we weighted the prognostic role of ENE in patients with lymph node-positive NSCLC. Two independent authors searched SCOPUS and PubMed through 28 February 2017. Prospective and retrospective studies on NSCLC, comparing patients with presence of ENE (ENE+) ENE+) vs. only intranodal extension (ENE-) and including data regarding prognosis, were considered as eligible. Data were summarized using risk ratios (RR) for the number of deaths/recurrences, and hazard ratios (HR) with 95% confidence intervals (CI) for time-dependent risk related to ENE+, adjusted for potential confounders. We identified 13 studies, including 1709 patients (573 ENE+ and 1136 ENE-) with a median follow-up of 60 months. ENE was associated with a significantly increased risk of mortality of all causes (RR = 1.39, 95% CI: 1.18-1.65, P < 0.0001, I2 = 70%; HR = 1.30, 95% CI: 1.01-1.67, P = 0.04, I2 = 0%) and of disease recurrence (RR = 1.32, 95% CI: 1.04-1.68, P = 0.02, I2 = 42%; HR = 1.93, 95% CI: 1.53-2.44, P < 0.0001, I2 = 0%). We conclude that in NSCLC, requirements for assessment of ENE should be included in gross sampling and ENE status should be included in the pathology report. Inclusion of ENE status in oncology staging systems will allow further assessment of its role as prognostic parameter.

Extranodal extension of lymph node metastasis is a marker of poor prognosis in oesophageal cancer: a systematic review with meta-analysis.

The extranodal extension (ENE) of nodal metastasis is the extension of neoplastic cells through the nodal capsule into the perinodal adipose tissue. This histological feature has recently been indicated as an important prognostic factor in different types of malignancies; in this manuscript, we aim at defining its role in the prognosis of oesophageal cancer with the tool of meta-analysis. Two independent authors searched SCOPUS and PubMed until 31 August 2015 without language restrictions. The studies with available data about prognostic parameters in subjects with oesophageal cancer, comparing patients with the presence of ENE (ENE+) versus only intranodal extension (ENE-), were considered as eligible. Data were summarised using risk ratios (RRs) for number of deaths/recurrences and HRs together with 95% CIs for time-dependent risk related to ENE+, adjusted for potential confounders. Fourteen studies were selected; they followed-up 1437 patients with oesophageal cancer for a median follow-up of 39.4 months. The presence of ENE was associated with a significantly increased risk of all-cause mortality (RR=1.33; 95% CI 1.18 to 1.50, p<0.0001, I2=49%; HR=2.72, 95% CI 2.03 to 3.64, p<0.0001, I2=0%), cancer-specific mortality (RR=1.35; 95% CI 1.14 to 1.59, p=0.001, I2=57%; HR=1.97, 95% CI 1.41 to 2.75, p<0.0001, I2=41%) and of risk of recurrence (RR=1.50, 95% CI 1.20 to 1.88, p<0.0001, I2=9%; HR=2.27, 95% CI 1.72 to 2.90, p<0.0001, I2=0%). On the basis of these results, in oesophageal cancer, ENE should be considered from the gross sampling to the pathology report, and in future oncological staging system.

Prognostic impact of extra-nodal extension in thyroid cancer: A meta-analysis.

BACKGROUND AND OBJECTIVES: Lymph node involvement is common in thyroid cancer, but the system of staging does not consider the histological features of lymph node metastases. We conducted a meta-analysis to investigate the prognostic role of extranodal extension (ENE) in thyroid cancer patients. METHODS: We ran PubMed and SCOPUS searches without language restrictions. Prospective studies reporting data on overall mortality, cancer-specific mortality, or disease recurrence including thyroid cancer patients, in which cases with ENE (ENE+) were compared with those with only intranodal disease (ENE-) were eligible. Data were summarized using risk ratios (RR) for number of deaths/recurrences, and hazard ratios (HR) for time-dependent risks related to ENE+ status, adjusted for potential confounders. RESULTS: Of 414 hits, 23 studies were eligible and included. Compared to ENE-, patients who were ENE+ had significantly higher rates of all-cause mortality (studies = 8; RR = 3.25; 95%CI: 1.35-2.64, I(2) = 83%) and recurrence (studies = 17; RR = 2.64, 95%CI: 1.93-3.60, I(2) = 73%). Using HRs adjusted for potential confounders, ENE+ status carried a significantly higher risk of all-cause and cancer-specific mortality and disease recurrence. CONCLUSION: It becomes mandatory to consider ENE in the histopathological examination of surgical samples in thyroid cancer patients, and this factor should be included in future oncological staging systems.

Surface-Regulated Nano-SnO2/Pt3Co/C Cathode Catalysts for Polymer Electrolyte Fuel Cells Fabricated by a Selective Electrochemical Sn Deposition Method.

We have achieved significant improvements for the oxygen reduction reaction activity and durability with new SnO2-nanoislands/Pt3Co/C catalysts in 0.1 M HClO4, which were regulated by a strategic fabrication using a new selective electrochemical Sn deposition method. The nano-SnO2/Pt3Co/C catalysts with Pt/Sn = 4/1, 9/1, 11/1, and 15/1 were characterized by STEM-EDS, XRD, XRF, XPS, in situ XAFS, and electrochemical measurements to have a Pt3Co core/Pt skeleton-skin structure decorated with SnO2 nanoislands at the compressive Pt surface with the defects and dislocations. The high performances of nano-SnO2/Pt3Co/C originate from efficient electronic modification of the Pt skin surface (site 1) by both the Co of the Pt3Co core and surface nano-SnO2 and more from the unique property of the periphery sites of the SnO2 nanoislands at the compressive Pt skeleton-skin surface (more active site 2), which were much more active than expected from the d-band center values. The white line peak intensity of the nano-SnO2/Pt3Co/C revealed no hysteresis in the potential up-down operations between 0.4 and 1.0 V versus RHE, unlike the cases of Pt/C and Pt3Co/C, resulting in the high ORR performance. Here we report development of a new class of cathode catalysts with two different active sites for next-generation polymer electrolyte fuel cells.