Synthesis of Metal-Nitrogen-Carbon Electrocatalysts with Atomically Regulated Nitrogen-Doped Polycyclic Aromatic Hydrocarbons.

Tuning the active site structure of metal-nitrogen-carbon electrocatalysts has recently attracted increasing interest. Herein, we report a bottom-up synthesis strategy in which atomically regulated N-doped polycyclic aromatic hydrocarbons (N-PAHs) of NxC42-x (x = 1, 2, 3, 4) were used as ligands to allow tuning of the active site's structures of M-Nx and establish correlations between the structures and electrocatalytic properties. Based on the synthesis process, detailed characterization, and DFT calculation results, active structures of Nx-Fe1-Nx in Fe1-Nx/RGO catalysts were constructed. The results demonstrated that the extra uncoordinated N atoms around the Fe1-N4 moieties disrupted the π-conjugated NxC42-x ligands, which led to more localized electronic state in the Fe1-N4 moieties and superior catalytic performance. Especially, the Fe1-N4/RGO exhibited optimized performance for ORR with E1/2 increasing by 80 mV and Jk at 0.85 V improved 18 times (compared with Fe1-N1/RGO). This synthesis strategy utilizing N-PAHs holds significant promise for enhancing the controllability of metal-nitrogen-carbon electrocatalyst preparation.

Long-Range Cationic Disordering Induces two Distinct Degradation Pathways in Co-Free Ni-Rich Layered Cathodes.

Ni-rich layered oxides are one of the most attractive cathode materials in high-energy-density lithium-ion batteries, their degradation mechanisms are still not completely elucidated. Herein, we report a strong dependence of degradation pathways on the long-range cationic disordering of Co-free Ni-rich Li1-m (Ni0.94 Al0.06 )1+m O2 (NA). Interestingly, a disordered layered phase with lattice mismatch can be easily formed in the near-surface region of NA particles with very low cation disorder (NA-LCD, m≤0.06) over electrochemical cycling, while the layered structure is basically maintained in the core of particles forming a "core-shell" structure. Such surface reconstruction triggers a rapid capacity decay during the first 100 cycles between 2.7 and 4.3 V at 1 C or 3 C. On the contrary, the local lattice distortions are gradually accumulated throughout the whole NA particles with higher degrees of cation disorder (NA-HCD, 0.06≤m≤0.15) that lead to a slow capacity decay upon cycling.

In Situ Synchrotron X-ray Diffraction Studies of the Mechanochemical Synthesis of ZnS from its Elements.

Invited for the cover of this issue is Claudia Weidenthaler and co-workers at the Max-Planck-Institut für Kohlenforschung, Shenzhen University and Deutsches Elektronen Synchrotron. The image depicts the X-ray diffraction results showing the formation of ZnS and the subsequent phase transition from the hexagonal to the cubic modification. Read the full text of the article at 10.1002/chem.202101260.

In Situ Synchrotron X-ray Diffraction Studies of the Mechanochemical Synthesis of ZnS from its Elements.

Mechanochemistry, as a synthesis tool for inorganic materials, became an ever-growing field in material chemistry. The direct energy transfer by collision of the educts with the milling media gives the possibility to design environmental-friendly reactions. Nevertheless, the underlying process of energy transfer and hence the kinetics of mechanosynthesis remain unclear. Herein, we present in situ synchrotron X-ray diffraction studies coupled with pressure measurements performed during the formation of ZnS and the subsequent phase transition (PT) from the hexagonal to the cubic modification. Milling Zn and S8 results in the sublimation of S8 , observed by a sudden pressure increase. Simultaneously, the hexagonal metastable ZnS-modification (wurtzite) forms. Via detection of the pressure maximum, the exact start of the wurtzite formation can be determined. Immediately after the formation of wurtzite, the structural PT to the thermodynamic stable cubic modification sphalerite takes place. This PT can be described by the Prout-Tompkins equation for autocatalytic reactions, similar to thermally induced PT in sulfur vapor at high temperatures (T>1133 K). The increase in the reactivity of the wurtzite formation is explained by the reaction in sulfur vapor and the induction of defect structures by the collisions with the milling media.

A Novel High-Pressure Tin Oxynitride Sn2 N2 O.

We report the first oxynitride of tin, Sn2 N2 O (SNO), exhibiting a Rh2 S3 -type crystal structure with space group Pbcn. All Sn atoms are in six-fold coordination, in contrast to Si in silicon oxynitride (Si2 N2 O) and Ge in the isostructural germanium oxynitride (Ge2 N2 O), which appear in four-fold coordination. SNO was synthesized at 20 GPa and 1200-1500 °C in a large volume press. The recovered samples were characterized by synchrotron powder X-ray diffraction and single-crystal electron diffraction in the TEM using the automated diffraction tomography (ADT) technique. The isothermal bulk modulus was determined as Bo =193(5) GPa by using in-situ synchrotron X-ray diffraction in a diamond anvil cell. The structure model is supported by DFT calculations. The enthalpy of formation, the bulk modulus, and the band structure have been calculated.

Gold on Different Manganese Oxides: Ultra-Low-Temperature CO Oxidation over Colloidal Gold Supported on Bulk-MnO2 Nanomaterials.

Nanoscopic gold particles have gained very high interest because of their promising catalytic activity for various chemicals reactions. Among these reactions, low-temperature CO oxidation is the most extensively studied one due to its practical relevance in environmental applications and the fundamental problems associated with its very high activity at low temperatures. Gold nanoparticles supported on manganese oxide belong to the most active gold catalysts for CO oxidation. Among a variety of manganese oxides, Mn2O3 is considered to be the most favorable support for gold nanoparticles with respect to catalytic activity. Gold on MnO2 has been shown to be significantly less active than gold on Mn2O3 in previous work. In contrast to these previous studies, in a comprehensive study of gold nanoparticles on different manganese oxides, we developed a gold catalyst on MnO2 nanostructures with extremely high activity. Nanosized gold particles (2-3 nm) were supported on α-MnO2 nanowires and mesoporous ß-MnO2 nanowire arrays. The materials were extremely active at very low temperature (-80 °C) and also highly stable at 25 °C (70 h) under normal conditions for CO oxidation. The specific reaction rate of 2.8 molCO·h(-1)·gAu(-1) at a temperature as low as -85 °C is almost 30 times higher than that of the most active Au/Mn2O3 catalyst.

Pulmonary embolism in a patient of tetralogy of Fallot: a diagnostic challenge.

A 46-year-old male patient with tetralogy of Fallot presented to the emergency department with progressive dyspnea for 3 days. The dyspnea was refractory to treatment for tet spells. Pulmonary embolism (PE) was subsequently diagnosed by computed tomography, and the patient was successfully treated with heparinization. Chronic hypoxemia-induced secondary polycythemia and the consequent increase in blood hyperviscosity predisposed this patient to PE. This case reminds us of the similarity in clinical presentation between PE and tet spells.

Electrochemically dealloyed nanoporous Fe40Ni20Co20P15C5 metallic glass for efficient and stable electrocatalytic hydrogen and oxygen generation.

The anion exchange membrane (AEM) in fuel cells requires new, stable, and improved electrocatalysts for large scale commercial production of hydrogen fuel for efficient energy conversion. Fe40Ni20Co20P15C5, a novel metallic glass ribbon, was prepared by arc melting and melt spinning method. The metallic glass was evaluated as an efficient electrocatalyst in water-splitting reactions, namely hydrogen evolution reaction under acidic and alkaline conditions. In addition, oxygen evolution reaction in alkaline medium was also evaluated. In 0.5 M H2SO4, the metallic glass ribbons, after electrochemical dealloying, needed an overpotential of 128 mV for hydrogen evolution reaction, while in 1 M KOH they needed an overpotential of 236 mV for hydrogen evolution. For the oxygen evolution reaction, the overpotential was 278 mV. The electrochemical dealloying procedure significantly reduced the overpotential, and the overpotential remained constant over 20 hours of test conditions under acidic and alkaline conditions. The improved electrocatalytic activity was explained based on the metastable nature of metallic glass and the synergistic effect of metal hydroxo species and phosphates. Based on the excellent properties and free-standing nature of these metallic glass ribbons in electrolyte medium, we propose the current metallic glass for commercial, industrial electrocatalytic applications.

Investigation of the Structural Heterogeneity and Corrosion Performance of the Annealed Fe-Based Metallic Glasses.

This study investigated the structural heterogeneity, mechanical property, electrochemical behavior, and passive film characteristics of Fe-Cr-Mo-W-C-B-Y metallic glasses (MGs), which were modified through annealing at different temperatures. Results showed that annealing MGs below the glass transition temperature enhanced corrosion resistance in HCl solution owing to a highly protective passive film formed, originating from the decreased free volume and the shrinkage of the first coordination shell, which was found by pair distribution function analysis. In contrast, the enlarged first coordination shell and nanoscale crystal-like clusters were identified for MGs annealed in the supercooled liquid region, which led to a destabilized passive film and thereby deteriorated corrosion resistance. This finding reveals the crucial role of structural heterogeneity in tuning the corrosion performance of MGs.

A Stimulus-Responsive Zinc-Iodine Battery with Smart Overcharge Self-Protection Function.

Zinc-iodine aqueous batteries (ZIABs) are highly attractive for grid-scale energy storage due to their high theoretical capacities, environmental friendliness, and intrinsic non-flammability. However, because of the close redox potential of Zn stripping/platting and hydrogen evolution, slight overcharge of ZIABs would induce drastic side reactions, serious safety concerns, and battery failure. A novel type of stimulus-responsive zinc-iodine aqueous battery (SR-ZIAB) with fast overcharge self-protection ability is demonstrated by employing a smart pH-responsive electrolyte. Operando spectroelectrochemical characterizations reveal that the battery failure mechanism of ZIABs during overcharge arises from the increase of electrolyte pH induced by hydrogen evolution as well as the consequent irreversible formation of insulating ZnO at anode and soluble Zn(IO3 )2 at cathode. Under overcharge conditions, the designed SR-ZIABs can be rapidly switched off with capacity degrading to 6% of the initial capacity, thereby avoiding continuous battery damage. Importantly, SR-ZIABs can be switched on with nearly 100% of capacity recovery by re-adjusting the electrolyte pH. This work will inspire the development of aqueous Zn batteries with smart self-protection ability in the overcharge state.

Improved kinetic behaviour of Mg(NH2)2-2LiH doped with nanostructured K-modified-LixTiyOz for hydrogen storage.

The system Mg(NH2)2 + 2LiH is considered as an interesting solid-state hydrogen storage material owing to its low thermodynamic stability of ca. 40 kJ/mol H2 and high gravimetric hydrogen capacity of 5.6 wt.%. However, high kinetic barriers lead to slow absorption/desorption rates even at relatively high temperatures (>180 °C). In this work, we investigate the effects of the addition of K-modified LixTiyOz on the absorption/desorption behaviour of the Mg(NH2)2 + 2LiH system. In comparison with the pristine Mg(NH2)2 + 2LiH, the system containing a tiny amount of nanostructured K-modified LixTiyOz shows enhanced absorption/desorption behaviour. The doped material presents a sensibly reduced (∼30 °C) desorption onset temperature, notably shorter hydrogen absorption/desorption times and reversible hydrogen capacity of about 3 wt.% H2 upon cycling. Studies on the absorption/desorption processes and micro/nanostructural characterizations of the Mg(NH2)2 + 2LiH + K-modified LixTiyOz system hint to the fact that the presence of in situ formed nanostructure K2TiO3 is the main responsible for the observed improved kinetic behaviour.

Deformations of Ti-6Al-4V additive-manufacturing-induced isotropic and anisotropic columnar structures: Insitu measurements and underlying mechanisms.

The deformations of isotropic and anisotropic Ti-6Al-4V columnar structures fabricated by additive manufacturing were extensively examined. The distinct texture and microstructure distributions were characterised. In situ X-ray diffraction measurements show different lattice activities resulting from the different microstructure distributions. Spatially resolved mapping revealed manufacturing-induced crystallite-orientation distributions that determine the deformation mechanisms. We propose a self-consistent model to correlate the multi-scale characteristics, from the anisotropic-texture-distribution microstructure to the bulk mechanical properties. We determined that basal and pyramidal slip activities were activated by tension deformation. The underlying additive-manufacturing-induced crystal plasticity plays a major role. We find that the texture development of the columnar structures and the distribution of crystallite orientation achieved by different processing conditions during additive manufacturing have important effects on the mechanical properties. The dominant deformation mode for the anisotropic Ti-6Al-4V columnar structure is basal slip, and that for the isotropic Ti-6Al-4V columnar structure is pyramidal slip. The difference may be important for determining the fatigue behaviour.

Serial cytokine levels in patients with severe sepsis.

OBJECTIVE AND DESIGN: The serial or dynamic changes of cytokine levels in severely septic patients, between shock and no shock, survivors and non-survivors are still unclear. METHODS: Seventy-six patients with severe sepsis were enrolled to our study. Plasma levels of interferon-gamma, interleukin (IL)-6, IL-10, IL-12 and transforming growth factor-beta1 from day 1 to day 7 were determined. RESULTS: IL-6 level in non-survivors was higher than that in survivors on day 1. IL-10 level in non-survivors was higher than that in survivors on day 1, 2, and 3. IL-6 level in shock patients was higher than that in non-shock patients on day 1, 2, 6 and 7. IL-10 level in shock patients was higher than that in non-shock patients from day 1 to day 7. Plasma time-course curves of IL-6 and IL-10 were different between survivors and non-survivors. Plasma time-course curve of IL-6 was different between patients with shock and without shock. Regression analysis found that IL-6 was correlated with IL-10 and shock. IL-10 was correlated with IL-6 and mortality. CONCLUSION: IL-6 and IL-10 were the key cytokines in the pathogenesis of severe sepsis. IL-6 was comparatively more associated with septic shock and IL-10 was comparatively more associated with mortality.

Comparing hydrocortisone and methylprednisolone in patients with septic shock.

INTRODUCTION: Intravenous hydrocortisone of 200-300 mg/day for 7 days is suggested for patients with septic shock who require vasopressors to maintain mean artery pressure >or=65 mmHg, despite adequate fluid resuscitation. No study to date has compared the effects between physiologic doses of hydrocortisone and methylprednisolone in patients with septic shock. METHODS: From July 2007 to June 2008, patients who were admitted to the intensive care unit at Chang Gung Memorial Hospital, Keelung, Taiwan, with low-dose steroid therapy due to septic shock were enrolled in this study. The typical steroid therapy included 7 days of intravenous hydrocortisone 50 mg every 6 hours. Methylprednisolone (20 mg every 12 hours) was replaced in these patients from January 2008 because no hydrocortisone could be prescribed. RESULTS: A total of 21 patients were prescribed hydrocortisone and 19 patients were prescribed methylprednisolone. The survival rates for patients receiving hydrocortisone were relatively higher compared with those receiving methylprednisolone, but the difference was not significant. There were no significant differences in the Kaplan-Meier curves for the time to reverse shock between patients who received hydrocortisone, or methylprednisolone. Further regression analysis showed no significant independent factors associated with the survival rates and the time to reverse shock among age, sex, Acute Physiology and Chronic Health Evaluation II (APACHE II) score, histories, and adverse events. CONCLUSIONS: Low-dose methylprednisolone and hydrocortisone might have a similar effect for the treatment of patients with septic shock.

Mortality of severe septic patients between physician's high and low care volumes.

BACKGROUND: Patients with severe sepsis frequently require intensive care unit (ICU) admission and different ICU care models may influence their outcomes. The mortality of severe septic patients between physician's high and low care volume remains unclear. METHODS: We analyzed the data from a three-year prospective observation study, which was performed in an adult medical ICU of Chung Gung Memorial Hospital, Keelung. The data included initial bundle therapies based on the Surviving Sepsis Campaign (SSC) guidelines for patients with severe sepsis. RESULTS: Clinical data of total 484 patients with severe sepsis were recorded. Cox regression model showed that physician's care volume was an independent factor for lowering mortality in ICU patients with severe sepsis (hazard ratio 0.708; 95% confidence interval 0.514-0.974; p = 0.034). Patients treated by high care volume physician had four out of nine bundle therapies that were significantly higher in percentage following the SSC guidelines. These four therapies were renal replacement therapy, administration of low-dose steroids for septic shock, prophylaxis of gastro-intestinal bleeding, and control of hyperglycemia. CONCLUSION: High care volume physician may decrease mortality in ICU patients with severe sepsis through fitting bundle therapies for sepsis.

The role of endothelial microparticles in autoimmune disease patients with Raynaud's phenomenon.

BACKGROUND AND AIM: Raynaud's phenomenon (RP) is a microvascular disorder characterized by episodic peripheral vasospasm and ischemia and is commonly found in patients with autoimmune diseases (AID). The vasomotor homoeostasis and endothelial cells damage are involved in RP. Endothelial microparticles (EMPs) may act as a biomarker for endothelial damage. The aim of this study is to investigate the correlation between the levels of microparticles (MPs) and microvasculopathy in AID with RP. METHODS: Thirty-seven patients with AID and RP (RP group) and 27 patients with AID but without RP (non-RP group) were enrolled. The microvasculopathy score of RP was graded by nailfold capillary microscopy. The plasma levels of MPs were measured by flow cytometry utilizing specific labels for endothelial MPs (CD105 and CD144) and annexin V staining for phosphatidylserine bearing-MPs (annexin V+MPs). RESULTS: The levels of circulating EMPs (CD105+ p = 0.005, CD144+ p = 0.004), and the annexin V+ MPs (p < 0.001) were significantly elevated in the RP group compared with the non-RP group. Moreover, the high microvasculopathy scores were closely related with annexinV+ MPs levels in the RP group (p = 0.041). CONCLUSIONS: Levels of circulating EMPs and annexin V+ MPs are elevated in AID patients with RP indicate the endothelial damage and endothelial dysfunctions. In addition, levels of annexin V+ MPs can predict the severity of microvasculopathy in AID with RP.

Outcomes of an emergency department intensive care unit in a tertiary medical center in Taiwan: An observational study.

PURPOSE: The boarding of critically ill patients in the emergency department (ED) could reduce quality of care and increase mortality. An ED intensive care unit (ICU) was set up in a 3715-bed medical center to facilitate timely delivery of critical care. This study reports comparative outcomes of EDICU patients with specialty ICU patients. MATERIALS AND METHODS: Medical records of adult nontrauma ED patients admitted to nonsurgical ICUs (EDICU, medical, cardiac, alimentary, and neurological units) between January 2007 and July 2011 were retrospectively reviewed. The respective number of admissions, bed turnover rate, and length of stay were compared. Cox regression models were also applied to compare inhospital mortality risks among these patients. RESULTS: With only 13% (14/108) of all ICU beds, EDICU admitted 36% (3711/10449) of patients. Emergency department ICU patients had an unfavorable adjusted hazard ratio for inhospital mortality compared with medical ICU and cardiac ICU patients, but after excluding patients with an ICU length of stay of 2 days or less, the difference in hazard ratio became nonsignificant. CONCLUSIONS: Emergency department ICU has admitted a disproportionately higher proportion of patients without sacrificing quality of care. Specialty care could be secured through direct communication between EDICU and specialty physicians and forming close collaboration between departments and ICUs.

Elevated circulating levels of tissue factor-positive microvesicles are associated with distant metastasis in lung cancer.

PURPOSE: Microvesicles (MV) in the blood stream are associated with distant metastasis in cancer. Platelet or endothelial cell-related MV actively participate in thrombogenesis, which is an important step in cancer metastasis. This study investigated the correlations between MV levels of platelet-poor plasma and distant metastasis in lung cancer. METHODS: Platelet-poor plasma from 44 treatment-naive lung cancer (23 with distant metastasis) and 19 normal subjects was used to determine the levels of glycoprotein Iß (CD42) + platelet MV (PMV), P-selectin (CD62P) + PMV, VE-cadherin (CD144) + endothelial MV (EMV), tissue factor (CD142) + MV, thrombin-antithrombin complex and vascular endothelial growth factor (VEGF). RESULTS: The level of CD142 + MV was significant (odds ratio 5.86, 95 % confidence interval 1.31-38.3) in predicting distant metastasis in lung cancer, and a cutoff value of 2.668 (after logarithm transformation) in the ROC curve had a specificity of 90 % and a sensitivity of 59 %. The presence of distant metastasis showed a significant correlation between CD144 + EMV and VEGF, but not between CD144 + EMV and CD42 + PMV or CD62P + PMV in lung cancer subjects. CONCLUSIONS: The finding of CD142 + MV in platelet-poor plasma may be useful for suggesting distant metastasis in lung cancer. In addition to thrombogenesis, interaction between VE-cadherin and VEGF may be needed for successful metastasis in lung cancer.

Functional haplotypes in the promoter region of transcription factor Nrf2 in chronic obstructive pulmonary disease.

Nuclear factor (erythroid-derived 2)-like 2 (Nrf2) protects against oxidative stress which is important in the pathogenesis of chronic obstructive pulmonary disease (COPD). Three single nucleotide polymorphisms and 1 triplet repeat polymorphism are found in the promoter region of the Nrf2 gene. Molecular haplotyping of the Nrf2 promoter region was performed using DNA obtained from the peripheral blood of 69 COPD patients. The luciferase activities of Nrf2 promoter constructs containing all possible combinations of the 4 polymorphisms were determined and found to differ among the 16 haplotypes.The haplotypes isolated from the subjects were divided into 3 groups (L: low; M: medium; H: high) on the basis of luciferase activities. The proportions of subjects belonging to global initiative for chronic obstructive lung disease stage 3 or 4 decreased from the group with the LL haplotype to that with the HH haplotype. Presence of the LH or MM haplotype (hazard ratio, 3.36; 95% confidence interval, 1.16-9.69), gender (0.13; 0.02-0.67), and post-bronchodilator FEV1 value of predicted (0.95; 0.91-0.99) are significant predictors of respiratory failure development.The haplotype of the Nrf2 gene promoter affects its activity, and is associated with the severity and the development of respiratory failure in COPD.