Reversible Dissociation of a Dialumene

Dialumenes are neutral Al(I) compounds with Al=Al multiple bonds. We report the isolation of an amidophosphine‐supported dialumene. Our X‐ray crystallographic, spectroscopic, and computational DFT analyses reveal a long and extreme trans‐bent Al=Al bond with a low dissociation energy and bond order. In solution, the dialumene can dissociate into monomeric Al(I) species. Reactivity studies reveal two modes of reaction: as dialumene or as aluminyl monomers

Practical colorimetry of 3-Nitro-1,2,4-Triazol-5-One

A field ready colorimetric method of quantifying the concentration of aqueous 3‐nitro‐1,2,4‐triazol‐5‐one (NTO), several orders of magnitude below its environmental toxicity level, has been developed. The test allows for the immediate evaluation of the level of contamination in aqueous solution without the need for analytical equipment such as high pressure liquid chromatography (HPLC). The observed colours have been explained by the different NTO species present over the range of pH; these observations are supported by modelling and experimental results

[Pd4(μ3-SbMe3)4(SbMe3)4]: A Pd(0) tetrahedron with μ3-bridging trimethylantimony ligands

The palladium(II) chlorostibine complex [PdCl2(SbMe2Cl)2]2 has a dimeric structure in the solid state, stabilized by hyper-coordination at the Lewis amphoteric Sb centers. Reaction with 8 equiv of MeLi forms [Pd4(μ3-SbMe3)4(SbMe3)4], whose structure comprises a tetrahedral Pd(0) core with four terminal SbMe3 ligands and four μ3-SbMe3 ligands, one capping each triangular Pd3 face. Density functional theory calculations, supported by energy decomposition analysis and the natural orbitals for chemical valence scheme, highlight significant donor and acceptor orbital contributions to the bonding between both the terminal and the bridging SbMe3 ligands and the Pd4 core

Direct oxide transfer from an η2-keto ligand to generate a cobalt PCcarbeneP(O) pincer complex

We report the direct carbonyl cleavage in a κ3-P′,(η2-C,O),P′′ ligand by a monomeric cobalt centre through metal–ligand cooperativity. C–O cleavage leads to the formation of a PCcarbeneP(O) pincer ligand with a central alkylidene anchor. A DFT analysis, supported by kinetic studies, suggests that decoordination of a pincer phosphino arm to generate a kinetically accessible free phosphine may be critical in transfer of the oxide to a phosphorus position. Thus, oxide transfer to bisphosphino bidentate co-ligands was also found to be viable, allowing access to the previously reported PCcarbeneP pincer complex (2), where bisphosphines were used as oxide sequestering agents

Asymmetric bis-PNP pincer complexes of zirconium and hafnium – a measure of hemilability

Asymmetrically-bound pyrrolide-based bis-PNP pincer complexes of zirconium and hafnium have been formed. The [κ2-PNPPh][κ3-PNPPh]MCl2 species are in direct contrast to previous zirconium PNP pincer complexes. The pincer ligands are fluxional in their binding and the energy barrier for exchange has been approximated using VT-NMR spectroscopy and the result validated by DFT calculations

Back To The Roots: Tree-Based Algorithms for Weakly Supervised Anomaly Detection

Weakly supervised methods have emerged as a powerful tool for model-agnostic anomaly detection at the Large Hadron Collider (LHC). While these methods have shown remarkable performance on specific signatures such as di-jet resonances, their application in a more model-agnostic manner requires dealing with a larger number of potentially noisy input features. In this paper, we show that using boosted decision trees as classifiers in weakly supervised anomaly detection gives superior performance compared to deep neural networks. Boosted decision trees are well known for their effectiveness in tabular data analysis. Our results show that they not only offer significantly faster training and evaluation times, but they are also robust to a large number of noisy input features. By using advanced gradient boosted decision trees in combination with ensembling techniques and an extended set of features, we significantly improve the performance of weakly supervised methods for anomaly detection at the LHC. This advance is a crucial step towards a more model-agnostic search for new physics.Comment: 11 pages, 9 figure

Toll-like receptor 4 in experimental kidney transplantation: early mediator of endogenous danger signals

The role of toll-like receptors (TLRs) has been described in the pathogenesis of renal ischemia/reperfusion injury, but data on the expression and function of TLR4 during renal allograft damage are still scarce. We analyzed the expression of TLR4 in an experimental rat model 6 and 28 days after allogeneic kidney transplantation in comparison to control rats and rats after syngeneic transplantation. On day 6, a significant induction in TLR4 expression - restricted to the glomerular compartment - was found in acute rejecting allografts only. TLR4 expression strongly correlated with renal function, and TLR4 induction was accompanied by a significant increase in CC chemokine expression within the graft as well as in urinary CC chemokine excretion. TLR4 induction may be caused by an influx of macrophages as well as TLR4-expressing intrinsic renal cells. Fibrinogen deposition in renal allografts correlated with renal TLR4 expression and may act as a potent stimulator of chemokine release via TLR4 activation. This study provides, for the first time, data about the precise intrarenal localization and TLR4 induction after experimental kidney transplantation. It supports the hypothesis that local TLR4 activation by endogenous ligands may be one pathological link from unspecific primary allograft damage to subsequent chemokine release, infiltration and activation of immune cells leading to deterioration of renal function and induction of renal fibrosis. Copyright (c) 2012 S. Karger AG, Base

Cinnamaldehydes: Synthesis, antibacterial evaluation, and the effect of molecular structure on antibacterial activity

trans-Cinnamaldehyde is a major component of Cinnamomum cassia and has been reported to give rise to antimicrobial properties in cinnamon spice. In order to better understand the relationship between the structure of trans-cinnamaldehyde and its antimicrobial role, fifteen structurally different trans-cinnamaldehyde derivatives were selected for study based on their predicted electrophilicities. Both synthesized and commercial transcinnamaldehyde derivatives were evaluated for their antibacterial activity, with modest mM activity levels found against both E. coli and S. aureus. An initial mechanism of action study, suggesting that the electrophilicity of the trans-cinnamaldehydes affects the antibacterial activity, was conducted as well as an exploration of their ability to alter bacterial cell wall integrity. In addition, in vivo toxicity levels were determined using the larvae of the greater wax moth, Galleria mellonella, with all derivatives tested showing low toxicity