Mechanistic studies on fast ligand substitution reactions of Pt(II) in different ionic liquids: role of solvent polarity and ion-pair formation

The effect of several imidazolium-based ionic liquids on the mechanism of a classical ligand substitution reaction of [Pt(terpyridine)Cl] (+) with thiourea was investigated. A detailed kinetic study as a function of the nucleophile concentration and temperature was undertaken under pseudo-first-order conditions using stopped-flow techniques. Polarity measurements were performed for the employed ionic liquids on the basis of solvatochromic effects, and they show similarities with conventional polar solvents. Density-functional theory calculations (RB3LYP/LANL2DZp) were employed to predict the ion-pair stabilization energy between the ionic components of the ionic liquids and/or between the anions of the ionic liquids and the cationic Pt (II) complex. These data illustrate how the anions of the ionic liquids can affect the investigated substitution reaction. In general, the substitution mechanism in ionic liquids was found to have an associative character similar to that in conventional solvents. The observed deviations reflect the influence of the ionic liquid on the interaction between the anionic component of the liquid and the positively charged complex.     

Gold(I)‐Catalyzed N‐Desulfonylative Amination versus N‐to‐O 1,5‐Sulfonyl Migration: A Versatile Approach to 1‐Azabicycloalkanes

Valuable 1‐azabicycloalkane derivatives have been synthesized through a novel gold(I)‐catalyzed desulfonylative cyclization strategy. An ammoniumation reaction of ynones substituted at the 1‐position with an N‐sulfonyl azacycle took place in the presence of a gold cation by intramolecular cyclization of the disubstituted sulfonamide moiety onto the triple bond. Depending on the size of the heterocyclic ring and substitution of the substrates, two unprecedented forms of nucleophilic attack on the sulfonyl group were exploited, that is, a N‐desulfonylation in the presence of an external protic O nucleophile (37–87 %, 10 examples) and a unique N‐to‐O 1,5‐sulfonyl migration (60–98 %, 9 examples).     

Quadratic programming and combinatorial minimum weight product problems

We present a fully polynomial time approximation scheme (FPTAS) for minimizing an objective (a ^T x + γ)(b ^T x + δ) under linear constraints A x ≤ d. Examples of such problems are combinatorial minimum weight product problems such as the following: given a graph G = (V,E) and two edge weights find an s − t path P that minimizes a(P)b(P), the product of its edge weights relative to a and b.      

An evaluation of selected global (Q)SARs/expert systems for the prediction of skin sensitisation potential

Skin sensitisation potential is an endpoint that needs to be assessed within the framework of existing and forthcoming legislation. At present, skin sensitisation hazard is normally identified using in vivo test methods, the favoured approach being the local lymph node assay (LLNA). This method can also provide a measure of relative skin sensitising potency which is essential for assessing and managing human health risks. One potential alternative approach to skin sensitisation hazard identification is the use of (Quantitative) structure activity relationships ((Q)SARs) coupled with appropriate documentation and performance characteristics. This represents a major challenge. Current thinking is that (Q)SARs might best be employed as part of a battery of approaches that collectively provide information on skin sensitisation hazard. A number of (Q)SARs and expert systems have been developed and are described in the literature. Here we focus on three models (TOPKAT, Derek for Windows and TOPS-MODE), and evaluate their performance against a recently published dataset of 211 chemicals. The current strengths and limitations of one of these models is highlighted, together with modifications that could be made to improve its performance. Of the models/expert systems evaluated, none performed sufficiently well to act as a standalone tool for hazard identification.     

Hsp90 inhibitors disrupt mitochondrial homeostasis in cancer cells

Hsp90 is a cytosolic molecular chaperone whose paralog in mitochondria, TRAP1, protects cells from oxidative stress. The recent study in Cell by Kang et al. now identifies the molecular components of the proapoptotic network regulated by TRAP1, that includes Hsp90. Targeting Hsp90/TRAP1 inhibitors to mitochondria induces rapid tumor cell-specific apoptosis.     

Infrared borescopic characterization of corona and conventional ignition for lean/dilute combustion in heavy-duty natural-gas engines

Natural gas (NG) is attractive for heavy-duty (HD) engines for reasons of cost stability, emissions, and fuel security. NG requires forced ignition, but conventional gasoline-engine ignition systems are not optimized for NG and are challenged to ignite mixtures that are lean or diluted with exhaust-gas recirculation (EGR). NG ignition is particularly difficult in large-bore engines, where it is more challenging to complete combustion in the time available. High-speed infrared (IR) in-cylinder imaging and image-derived quantitative metrics were used to compare two ignition systems in terms of the early flame-kernel development and cycle-to-cycle variability (CCV) in a heavy-duty, natural-gas-fueled engine that had been modified to enable exhaust-gas recirculation and to provide optical access via borescopes. Imaging in the near IR and short-wavelength IR yielded strong signals from the water emission lines, which acted as a proxy for flame front and burned-gas regions while obviating image intensification (which can reduce spatial resolution). The ignition systems studied were a conventional system and a high-frequency corona system. The air/fuel mixtures investigated included stoichiometric without dilution and lean with EGR. The corona system produced five separate elongated, irregularly shaped, nonequilibrium-plasma streamers, leading to immediate formation of five spatially distinct wrinkled flame kernels around each streamer. Compared to the conventional spark ignition, which produces a single flame kernel that exhibits an initial laminar growth regime before wrinkling, corona ignition's early achievement of higher flame surface areas significantly shortened the ignition delay, resulting in reduced overall combustion duration and CCV for each mixture. Additionally, although the lean, dilute mixture produced higher CCV than the stoichiometric, minimally diluted mixture with both igniters, the mixtures ignited by the corona system suffered less than those ignited by the conventional system. Image-based measurements of CCV agreed with those based on in-cylinder pressure.     

Magic alkali-fullerene compound clusters of extreme thermal stability

The thermal stability of free pure C60-, as well as C60-alkali, and -alkaline-earth metal compound clusters is investigated. We find that small (C60)m-clusters (m相似文献