Operando XANES Reveals the Chemical State of Iron-Oxide Monolayers During Low-Temperature CO Oxidation.

We have used grazing incidence X-ray absorption near edge spectroscopy (XANES) to investigate the behavior of monolayer FeO films on Pt(111) under near ambient pressure CO oxidation conditions with a total gas pressure of 1 bar. Spectra indicate reversible changes during oxidation and reduction by O and CO at 150 °C, attributed to a transformation between FeO bilayer and FeO trilayer phases. The trilayer phase is also reduced upon heating in CO+O , consistent with a Mars-van-Krevelen type mechanism for CO oxidation.

Hydride formation and dynamic phase changes during template-assisted Pd electrodeposition.

We investigated the structural evolution of electrochemically fabricated Pd nanowiresby means of grazing-incidence transmission small- and wide-angle x-ray scattering (GTSAXS and GTWAXS), x-ray fluorescence (XRF) and two-dimensional surface optical reflectance (2D-SOR). This shows how electrodeposition and the hydrogen evolution reaction (HER) compete and interact during Pd electrodepositon. During the bottom-up growth of the nanowires, we show that-phase Pd hydride is formed.

: a high-energy surface X-ray diffraction analysis toolkit.

This work introduces the high-energy surface X-ray diffraction analysis toolkit (), an open-source cross-platform software package written in Python to allow the extraction and processing of high-energy surface X-ray diffraction (HESXRD) data sets. Thousands of large-area detector images are collected in a single HESXRD scan, corresponding to billions of pixels and hence reciprocal space positions. is an optimized reciprocal space binner that implements a graphical user interface to allow the easy and interactive exploration of HESXRD data sets.

Templated electrodeposition as a scalable and surfactant-free approach to the synthesis of Au nanoparticles with tunable aspect ratios.

A high-throughput method for the fabrication of ordered arrays of Au nanoparticles is presented. It is based on pulsed electrodeposition into porous anodic alumina templates. In contrast to many synthesis routes, it is cyanide-free, prior separation of the alumina template from the aluminium substrate is not required, and the use of contaminating surfactants/capping agents often found in colloidal synthesis is avoided.

Fifteen-minute consultation: Airway management in the acutely unwell child requiring intubation for the general paediatrician.

Emergency endotracheal intubation is a high risk procedure in acutely unwell children and is commonly jointly managed by paediatricians and anaesthetists. This article aims to develop a shared understanding of the practicalities and language around the risk factors for difficult intubation and management of failed intubation, including the approach to situations where you cannot intubate and or cannot ventilate, to improve communication and team working between these dynamic interdisciplinary teams.

Quantitative powder diffraction using a (2 + 3) surface diffractometer and an area detector.

X-ray diffractometers primarily designed for surface X-ray diffraction are often used to measure the diffraction from powders, textured materials and fiber-texture samples in 2θ scans. Unlike in high-energy powder diffraction, only a fraction of the powder rings is typically measured, and the data consist of many detector images across the 2θ range. Such diffractometers typically scan in directions not possible on a conventional laboratory diffractometer, which gives enhanced control of the scattering vector relative to the sample orientation.

Reflectance Microscopy on Polycrystalline Surfaces in Thermal Catalysis, Electrocatalysis, and Corrosion.

We have developed a microscope with a spatial resolution of 5 μm, which can be used to image the two-dimensional surface optical reflectance (2D-SOR) of polycrystalline samples in conditions. Within the field of surface science, tools that give information about the surface structure or chemistry of a sample under realistic experimental conditions have proven to be very valuable to understand the intrinsic reaction mechanisms in thermal catalysis, electrocatalysis, and corrosion science. To study heterogeneous surfaces , the experimental technique must both have spatial resolution and be able to probe through gas or electrolyte.

An electrochemical cell for 2-dimensional surface optical reflectance during anodization and cyclic voltammetry.

We have developed an electrochemical cell for in situ 2-Dimensional Surface Optical Reflectance (2D-SOR) studies during anodization and cyclic voltammetry. The 2D-SOR signal was recorded from electrodes made of polycrystalline Al, Au(111), and Pt(100) single crystals. The changes can be followed at a video rate acquisition frequency of 200 Hz and demonstrate a strong contrast between oxidizing and reducing conditions.

Multicentric Analytical and Inter-observer Comparability of Four Clinically Developed Programmed Death-ligand 1 Immunohistochemistry Assays in Advanced Clear-cell Renal Cell Carcinoma.

Background: Previous studies have suggested increased clinical benefit with inhibition of programmed death-ligand 1 (PD-L1)/programmed death-1 in patients with PD-L1-positive locally advanced/metastatic renal cell carcinoma (RCC). We examined the analytical and inter-observer comparability of PD-L1-positivity across 4 clinically developed immunohistochemistry assays in clear-cell RCC (CCRCC).

Materials And Methods: Randomly selected archived, formalin-fixed, paraffin-embedded nephrectomy specimens from 201 patients with locally advanced CCRCC were screened using VENTANA SP142.

Observing growth under confinement: Sn nanopillars in porous alumina templates.

Using a micro-focused high-energy X-ray beam, we have performed time-resolved depth profiling during the electrochemical deposition of Sn into an ordered porous anodic alumina template. Combined with micro-diffraction we are able to follow the variation of the structure at the atomic scale as a function of depth and time. We show that Sn initially deposits at the bottom of the pores, and forms metallic nanopillars with a preferred [100] orientation and a relatively low mosaicity.

Ki-67 (30-9) scoring and differentiation of Luminal A- and Luminal B-like breast cancer subtypes.

Introduction: Ki-67 labeling index assessed by immunohistochemical assays has been shown useful in assessing the risk of recurrence for estrogen receptor (ER)-positive HER2-negative breast cancers (BC) and distinguishing Luminal A-like from Luminal B-like tumors. We aimed to assess the performance of the Ventana CONFIRM anti-Ki-67 (30-9) Rabbit Monoclonal Primary Antibody.

Methods: We constructed a case-cohort design based on a random sample (n = 679) of all patients operated on for a first primary, non-metastatic, ER-positive, HER2-negative BC at the European Institute of Oncology (IEO) Milan, Italy during 1998-2002 and all additional patients (n = 303) operated during the same period, who developed an event (metastasis in distant organs or death due to BC as primary event) and were not included in the previous subset.

E-cadherin clone 36 nuclear staining dictates adverse disease outcome in lobular breast cancer patients.

Breast cancer is a heterogeneous disease and additional biomarkers for individually predicting patient outcomes are needed. Aberrant membrane E-cadherin immunoexpression has been demonstrated in lobular breast cancer. Also, E-cadherin nuclear staining has been reported, associating with prognosis in various tumors.

Adsorption, surface relaxation and electrolyte structure at Pt(111) electrodes in non-aqueous and aqueous acetonitrile electrolytes.

In situ electrochemical surface X-ray diffraction was employed to investigate the atomic scale structure of the electrochemical double layer and the relaxation at the Pt(111) electrode surface in non-aqueous and aqueous acetonitrile electrolytes under potential control. The X-ray measurements provide insight into the potential-dependence of the interface structure by combining potentiodynamic measurements (X-ray voltammetry) with potentiostatic measurements (crystal truncation rod data) to probe both the metal and electrolyte sides of the interface. The crystal truncation rod measurements are consistent with the potential dependent reorientation of acetonitrile in the absence of water and a parallel arrangement in the presence of water.

Self-organization of porous anodic alumina films studied by grazing-incidence transmission small-angle X-ray scattering.

Self-ordered porous anodic alumina (PAA) films are studied extensively due to a large number of possible applications in nanotechnology and low cost of production. Whereas empirical relationships between growth conditions and produced oxides have been established, fundamental aspects regarding pore formation and self-organization are still under debate. We present structural studies of PAA films using grazing-incidence transmission small-angle X-ray scattering.

Vancomycin-associated nephrotoxicity in the critically ill: a retrospective multivariate regression analysis*.

Objectives: To evaluate the influence of vancomycin dose, serum trough concentration, and dosing strategy on the evolution of acute kidney injury in critically ill patients.

Design: Retrospective, single-center, observational study.

Setting: University Hospital ICU, Birmingham, UK.

New evidence suggests pyroclastic flows are responsible for the remarkable preservation of the Jehol biota.

The lower Cretaceous Yixian and Jiufotang formations contain numerous exceptionally well-preserved invertebrate, vertebrate and plant fossils that comprise the Jehol Biota. Freshwater and terrestrial fossils of the biota usually occur together within some horizons and have been interpreted as deposits of mass mortality events. The nature of the events and the mechanisms behind the exceptional preservation of the fossils, however, are poorly understood.

BN/CC isosteric compounds as enzyme inhibitors: N- and B-ethyl-1,2-azaborine inhibit ethylbenzene hydroxylation as nonconvertible substrate analogues.

Good substrate gone bad! BN/CC isosterism of ethylbenzene leads to N-ethyl-1,2-azaborine and B-ethyl-1,2-azaborine. In contrast to ethylbenzene, which is the substrate for ethylbenzene dehydrogenase (EbDH), N-ethyl-1,2-azaborine (see scheme; Fc=Ferricenium tetrafluoroborate) and B-ethyl-1,2-azaborine are strong inhibitors of EbDH. Thus, the changes provided by BN/CC isosterism can lead to new biochemical reactivity.

Thermodynamically Controlled, Dynamic Binding of Diols to a 1,2-BN Cyclohexane Derivative.

The reversible covalent binding of diols to an -Bn 1,2-BN cyclohexane has been studied by B and H NMR spectroscopy and single-crystal X-ray diffraction analysis. The activation barrier for the reversible B-N Lewis acid-base interaction has been measured by variable-temperature NMR with bound (2,3)-(-)-2,3-butanediol ( = -40 °C, Δ = 11.2 ± 0.

Discovery of the first non-ATP competitive IGF-1R kinase inhibitors: advantages in comparison with competitive inhibitors.

A new series of IGF-1R inhibitors related to hydantoins were identified from a lead originating from HTS. Their noncompetitive property as well as their slow binding characteristics provided a series of compounds with unique selectivity and excellent cellular activities.

Service user involvement in cancer care: the impact on service users.

Background: Service user involvement is embedded in the United Kingdom's National Health Service, but knowledge about the impact of involvement on service users, such as the benefits and challenges of involvement, is scant. Our research addresses this gap.

Objective: To explore the personal impact of involvement on the lives of service users affected by cancer.

Dual role of human cytochrome P450 3A4 residue Phe-304 in substrate specificity and cooperativity.

The structural basis of cooperativity of progesterone hydroxylation catalyzed by human cytochrome P450 3A4 has been investigated. A recent study suggested that substitution of larger side chains at positions Leu-211 and Asp-214 partially mimics the action of effector by reducing the size of the active site. Based on predictions from molecular modeling that Phe-304 in the highly conserved I helix is involved in both effector and substrate binding, a tryptophan residue was substituted at this position.

2,2',3,3',6,6'-hexachlorobiphenyl hydroxylation by active site mutants of cytochrome P450 2B1 and 2B11.

The structural basis of species differences in cytochrome P450 2B-mediated hydroxylation of 2,2',3,3',6,6'-hexachlorobiphenyl (236HCB) was evaluated by using 14 site-directed mutants of cytochrome P450 2B1 and three point mutants of 2B11 expressed in Escherichia coli. To facilitate metabolite identification, seven possible products, including three hydroxylated and four dihydroxylated hexachlorobiphenyls, were synthesized by direct functionalization of precursors and Ullmann and crossed Ullmann reactions. HPLC and GC/MS analysis and comparison with authentic standards revealed that 2B1, 2B11, and all their mutants produced 4, 5-dihydroxy-236HCB and 5-hydroxy-236HCB, while 2B11 L363V and 2B1 I114V mutants also catalyzed hydroxylation at the 4-position.

Use of the steroid derivative RPR 106541 in combination with site-directed mutagenesis for enhanced cytochrome P-450 3A4 structure/function analysis.

RPR 106541 (20R-16alpha,17alpha-[butylidenebis(oxy)]-6al pha, 9alpha-difluoro-11beta-hydroxy-17beta-(methylthio)androst a-4-en-3-one) is an airway-selective steroid developed for the treatment of asthma. Two metabolites produced by human liver microsomes were identified as R- and S-sulfoxide diastereomers based on liquid chromatography/mass spectrometry analysis, proton nuclear magnetic resonance, and cochromatography with standards. Sulfoxide formation was determined to be cytochrome P-450 (CYP) 3A4-dependent by correlation with CYP3A4-marker nifedipine oxidase activity, inhibition by cyclosporin A and troleandomycin, and inhibition of R- (70%) and S- (64%) sulfoxide formation by anti-3A antibody.