Convergence of hormones and autoinducers at the host/pathogen interface

Most living organisms possess sophisticated cell-signaling networks in which lipid-based signals modulate biological effects such as cell differentiation, reproduction and immune responses. Acyl homoserine lactone (AHL) autoinducers are fatty acid-based signaling molecules synthesized by several Gram-negative bacteria that are used to coordinate gene expression in a process termed “quorum sensing” (QS). Recent evidence shows that autoinducers not only control gene expression in bacterial cells, but also alter gene expression in mammalian cells. These alterations include modulation of proinflammatory cytokines and induction of apoptosis. Some of these responses may have deleterious effects on the host’s immune response, thereby leading to increased bacterial pathogenesis. Prokaryotes and eukaryotes have cohabited for approximately two billion years, during which time they have been exposed to each others’ soluble signaling molecules. We postulate that organisms from the different kingdoms of nature have acquired mechanisms to sense and respond to each others signaling molecules, and we have named this process interkingdom signaling. We further propose that autoinducers, which exhibit structural and functional similarities to mammalian lipid-based hormones, are excellent candidates for mediating this interkingdom communication. Here we will compare and contrast bacterial QS systems with eukaryotic endocrine systems, and discuss the mechanisms by which autoinducers may exploit mammalian signal transduction pathways.     

Using block designs in crossing number bounds

The crossing number $\mathrm{\text{CR}}\left(G\right)$ of a graph $G=\left(V,E\right)$ is the smallest number of edge crossings over all drawings of $G$ in the plane. For any $k\ge 1$, the $k$‐planar crossing number of $G,{\mathrm{\text{CR}}}_k\left(G\right)$, is defined as the minimum of $\text{CR}\left(G_1\right)+\text{CR}\left(G_2\right)+?+\text{CR}\left(G_k\right)$ over all graphs $G_1,G_2,\dots ,G_k$ with ${\cup }_{i=1}^k{G}_i=G$. Pach et al [Comput. Geom.: Theory Appl. 68 (2018), pp. 2–6] showed that for every $k\ge 1$, we have ${\text{CR}}_k\left(G\right)\le (2/k^2?1/k^3)\text{CR}\left(G\right)$ and that this bound does not remain true if we replace the constant $2/k^2?1/k^3$ by any number smaller than $1/k^2$. We improve the upper bound to $(1/k^2)\left(1+o\left(1\right)\right)$ as $k\to \infty$. For the class of bipartite graphs, we show that the best constant is exactly $1/k^2$ for every $k$. The results extend to the rectilinear variant of the $k$‐planar crossing number.     

Development of an automated in situ fracture stage for a ToF‐SIMS system

The design philosophy and implementation of an ultra high vacuum (UHV), PC controlled, automated in situ fracture stage for a surface analysis system is described. ToF‐SIMS spectra are shown to illustrate the improvement in spectral quality obtained from micro‐compact tension (CT) tests of polymer matrix fracture surfaces produced using the fracture stage in UHV compared to those obtained from a sample tested at air. This system is flexible in that by changing the capacity of the load cell it is possible to reduce or increase maximum loads as the specimen type and material demands. The stage has been designed with instrumental flexibility in mind, utilising commercial SEM‐stub type sample mounts, and can thus be used for AES/SAM and XPS investigations, as well as ToF‐SIMS analysis, in the authors' laboratory. Copyright © 2008 John Wiley & Sons, Ltd.     

Comparative experimental and EXAFS studies in the Mizoroki-Heck reaction with heteroatom-functionalised N-heterocyclic carbene palladium catalysts

A study on the Mizoroki-Heck coupling of selected aryl bromides with acrylates catalysed by a series of Pd complexes of bidentate pyridyl-, picolyl-, diphenylphosphinoethyl- and diphenylphosphinomethyl-functionalised N-heterocyclic carbene (NHC) is reported. The observed activity is dependent on the type of solvent and base used and the nature of the "classical" donors of the mixed-donor bidentate ligand and its bite angle. A mechanistic model is presented for the pyridine-functionalised NHC complexes based on an in situ EXAFS study under dilute catalyst conditions (2 mM Pd). The model involves pre-dissociation of the pyridine functionality and oxidative addition of ArBr in the early stages of the reaction, as well as formation of monomeric and dimeric Pd species at the time of substrate conversion.     

Platinum catalysed 3,4- and 1,4-diboration of alpha,beta-unsaturated carbonyl compounds using bis-pinacolatodiboron

Bis-pinacolatodiboron reacts with [small alpha],[small beta]-unsaturated carbonyl compounds to give 1,4- and unprecedented 3,4-additions in the presence of a second generation Pt(0) catalyst at ambient temperature.     

3‐tert‐Butyl‐1‐(2‐pyridyl­methyl)‐3H‐imidazolium bromide hydrate

The structure of the title compound, C₁₃H₁₈N₃⁺·Br^?·H₂O, shows that the cation and the bromide anion are linked via the water mol­ecule through weak intermolecular hydrogen bonds. The water was not detected by NMR spectroscopy, but the cell content is in agreement with the elemental analysis. The presence of water plays an important role in further reactions.