Deoxygenation of Sulfoxides to Sulfides with Thionyl Chloride and Triphenylphosphine: Competition with the Pummerer Reaction

Although a number of methods have been developed to reduce sulfoxides to sulfides, many of these processes are limited by side reactions, low yields, poorly available reagents, or harsh reaction conditions. We recently studied the reaction of various sulfoxides with SOCl₂ and Ph₃P. We were able to obtain the corresponding sulfides in excellent yields (>90%) when aliphatic and aromatic sulfoxides were treated with SOCl₂ as a catalyst and Ph₃P in THF at room temperature

Latrunculin treatment abolishes F-actin coating of fused granules.

<p>(<b>A</b>) Low magnification images show complex lumens, identified by SRB (red) and Lifeact-EGFP fluorescence (green), lying between the cells within a pancreatic fragment. (<b>Ai</b>) is an image taken before the appearance of exocytic events, (<b>Av</b>) is taken after, at the time points “i” and “v” as indicated on the graph in panel (<b>C</b>). (<b>B</b>) Shows an image sequence from an enlarged region (box shown in A) of Lifeact-EGFP and SRB and the overlay, for a single exocytic event. The images were taken at the time points i, ii, iii, iv, and v as indicated on the graph in panel (<b>C</b>). (<b>C</b>) Is a graph of fluorescence changes over time taken from a region of interest placed over the exocytic event (indicated by an arrow). SRB fluorescence is plotted normalized to the first, rapid peak and shows a rapid rise followed by a slower increase. The simultaneously recorded Lifeact-EGFP signal, plotted as arbitrary fluorescence units, shows only very small changes over time.</p

F-actin coating is initiated simultaneously across the whole of the granule.

<p>(A) a high magnification image sequence (i, ii, iii, iv, v with times shown on graph in <b>B</b>) shows SRB entry and Lifeact-EGFP tracking of F-actin coating of an fusing individual granule. (<b>B</b>) Regions of interest (boxes a, b, c shown in <b>A</b>) placed around single fusing granules showed only small temporal differences in the time-course of F-actin coating. When fitted to a single exponential the τ values were 15.5, 13.3 and 15.5 seconds (for regions a, b, c respectively). (<b>C</b>) shows the graph obtained from the means of 10 events. The mean SRB signal from each granule is shown for reference (black plot). For each event regions a and b were placed at the luminal-granule interface and c was placed at the top of the granule. The extreme minima (labelled min) and maxima (labelled max) of the SEM from all 3 regions of interest are shown as dotted grey lines. The average Lifeact-EGFP change within each region was fitted to a single exponential and these fitted curves are shown, colour-coded, on the graph.</p

F-actin coats individual fused granules.

<p>Pancreatic tissue fragments were bathed in paraformaldehyde-fixable fluorescein extracellular dye and then stimulated with 1 µM acetylcholine. Each fused granule is then identified by the uptake of fluorescent dye. After fixation, co-staining with phalloidin Alexa-633, shows that each fused granule is coated with F-actin. The upper panel shows a low magnification image, where-as the lower panel shows high magnification images that are enlargements of the boxed region.</p

Lifeact-EGFP transgenic mice show similar acetylcholine-induced exocytic responses to wild type.

<p>(<b>A</b>) The images were taken before (0 s) and 300 s after exocytic fusion induced by 1 µM acetylcholine stimulation of mouse pancreatic fragments in wild type (upper images) and Lifeact-EGFP transgenic animals (lower images). The tissue fragments were bathed in extracellular fluorescent dye (SRB) which labels the lumens (bright fluorescence between the cells in control) and enters and labels each individual granule (bright fluorescent spots along the lumen after 300 s). (<b>B</b>) We identify the time point of appearance of each fusing granule (cumulative histogram, aligned to the first exocytic event) which shows both wild type and transgenic animals have a similar time-course and extent of exocytic response. (C) Further, we compare the fluorescence profile, over time, of SRB dye entry into each individual granule and observe no differences between wild type and transgenic animals.</p

Real-time imaging of exocytic fusion events and F-actin coating.

<p>(<b>A</b>) Low magnification images show a lumen lying diagonally between two acinar cells identified with SRB (red) and Lifeact-EGFP (green) in the sub-apical region. (<b>A, i</b>) is an image taken before the appearance of exocytic events at the time point indicated “i” on the graph of fluorescence intensity over time in panel (<b>C</b>). (<b>A, v</b>) Is an image at a time point after induction of a number of exocytic events which can be seen as bright spots of SRB fluorescence along the lumen; the time point “v” is indicated on the lower graph (<b>C</b>). (<b>B</b>) Shows an image sequence from an enlarged region (box shown in <b>A</b>) of Lifeact-EGFP and SRB and the overlay, for two exocytic events. The images were taken at the time points i, ii, iii, iv, and v as indicated on the graph in panel (<b>C</b>). (<b>C</b>) is a graph of fluorescence changes over time taken from a region of interest placed over the lower exocytic event (indicated by an arrowhead). SRB fluorescence is plotted normalized to the peak and rises rapidly to a peak and then decays to a plateau. The simultaneously recorded Lifeact-EGFP signal, plotted in arbitrary fluorescence units, rises slowly and nearly reaches a maximum by the end of the record. The starting points of the SRB and Lifeact-EGFP signals, as determined by a positive deflection of the signal by more than 5 times the standard deviation of the signal noise, are shown by the colour-coded triangles on the X axis. The black dotted lines were mono-exponential fits to the data with τ values of 6.9 s (SRB) and 29.4 s (Lifeact-EGFP).</p

Fluorine-free Plasma Enhanced Atomic Layer Deposited Ultrathin Tungsten Nitride Thin Films for Dual Diffusion Barrier Performance

A vacuum deposition technique in a highly narrow device is a critical issue for fabricating barrier layers in semiconductor devices. Though tungsten nitride (WNx) thin films’ uniform and conformal thickness control can be achieved via atomic layer deposition (ALD), most ALD-WNx processes use fluorine-based precursors, resulting in high resistivity with low growth rate and corrosive and toxic F-containing impurities. This study underscores the importance of the plasma-enhanced ALD (PEALD) process for WNx films via a fluorine-free inorganic WCl5 precursor and critically optimizes the counter reactant ratio (N2 + H2 ratio of 1:1 to 1:10), temperature ranges (200∼325 °C), plasma mixture, plasma power, and postannealing condition process parameters. The as-grown WNx film properties and the impact of the plasma ratio on the WN phase, crystallinity, and stoichiometry were confirmed comprehensively by advanced transmission electron microscopy, spectroscopy, and diffraction techniques. Notably, secondary ion mass and photoelectron spectroscopies ensure uniformity and fewer impurity contents of O/Cl throughout the thickness of the WNx film. Significantly, the parent nanocrystalline hexagonal WN phase at a N2 + H2 ratio of 1:3 at 250 °C transformed to a crystalline cubic W2N phase with decreasing resistivity as the H2 ratio of total N2 + H2 mixture plasma gas increased. The postannealed (500 °C) deposited WNx film demonstrated the formation of a stable cubic phase, lowering the sheet resistance with increasing deposition temperature (film thickness) and plasma ratio. The as-deposited film’s diffusion barrier performance against Cu and Ru (∼4 nm) was evaluated to withstand up to 850 °C, revealing a promising dual diffusion barrier capability as interconnects in challenging shrinking semiconductor device structures

Preparation and Analysis of Bicyclic Polystyrene

Bicyclic polystyrene was prepared by combining atom transfer radical polymerization and click chemistry. The bicyclic polymer was separated from concurrently produced acyclic (branched) polymers through fractional precipitation, and its purity was quantified by two-dimensional liquid chromatography analysis. The structure of bicyclic polymer was characterized by SEC, MALDI–TOF MS, ¹H NMR, and FT-IR

Data_Sheet_1_Integrative analysis of RNA-sequencing and microarray for the identification of adverse effects of UVB exposure on human skin.docx

BackgroundUltraviolet B (UVB) from sunlight represents a major environmental factor that causes toxic effects resulting in structural and functional cutaneous abnormalities in most living organisms. Although numerous studies have indicated the biological mechanisms linking UVB exposure and cutaneous manifestations, they have typically originated from a single study performed under limited conditions.MethodsWe accessed all publicly accessible expression data of various skin cell types exposed to UVB, including skin biopsies, keratinocytes, and fibroblasts. We performed biological network analysis to identify the molecular mechanisms and identify genetic biomarkers.ResultsWe interpreted the inflammatory response and carcinogenesis as major UVB-induced signaling alternations and identified three candidate biomarkers (IL1B, CCL2, and LIF). Moreover, we confirmed that these three biomarkers contribute to the survival probability of patients with cutaneous melanoma, the most aggressive and lethal form of skin cancer.ConclusionOur findings will aid the understanding of UVB-induced cutaneous toxicity and the accompanying molecular mechanisms. In addition, the three candidate biomarkers that change molecular signals due to UVB exposure of skin might be related to the survival rate of patients with cutaneous melanoma.</p

Proteasome Inhibitors with Pyrazole Scaffolds from Structure-Based Virtual Screening

We performed a virtual screen of ∼340 000 small molecules against the active site of proteasomes followed by in vitro assays and subsequent optimization, yielding a proteasome inhibitor with pyrazole scaffold. The pyrazole-scaffold compound displayed excellent metabolic stability and was highly effective in suppressing solid tumor growth in vivo. Furthermore, the effectiveness of this compound was not negatively impacted by resistance to bortezomib or carfilzomib