How metallylenes activate small molecules

We have studied the activation of dihydrogen by metallylenes using relativistic density functional theory (DFT). Our detailed activation strain and Kohn–Sham molecular orbital analyses have quantified the physical factors behind the decreased reactivity of the metallylene on going down Group 14, from carbenes to stannylenes. Along this series, the reactivity decreases due to a worsening of the back-donation interaction between the filled lone-pair orbital of the metallylene and the σ*-orbital of H₂, which, therefore, reduces the metallylene–substrate interaction and increases the reaction barrier. As the metallylene ligand is varied from nitrogen to phosphorus to arsenic a significant rate enhancement is observed for the activation of H₂ due to (i) a reduced steric (Pauli) repulsion between the metallylene and the substrate; and (ii) less activation strain, as the metallylene becomes increasingly more predistorted. Using a rationally designed metallylene with an optimal Group 14 atom and ligand combination, we show that a number of small molecules (i.e. HCN, CO₂, H₂, NH₃) may also be readily activated. For the first time, we show the ability of our H₂ activated designer metallylenes to hydrogenate unsaturated hydrocarbons. The results presented herein will serve as a guide for the rational design of metallylenes toward the activation of small molecules and subsequent reactions.

Quantum chemical analyses reveal how model metallylene catalysts activate H₂. This is the first step towards the rational design of metallylenes for the activation of small molecules and subsequent reactions.     

GeneMCL in microarray analysis

Accurately and reliably identifying the actual number of clusters present with a dataset of gene expression profiles, when no additional information on cluster structure is available, is a problem addressed by few algorithms. GeneMCL transforms microarray analysis data into a graph consisting of nodes connected by edges, where the nodes represent genes, and the edges represent the similarity in expression of those genes, as given by a proximity measurement. This measurement is taken to be the Pearson correlation coefficient combined with a local non-linear rescaling step. The resulting graph is input to the Markov Cluster (MCL) algorithm, which is an elegant, deterministic, non-specific and scalable method, which models stochastic flow through the graph. The algorithm is inherently affected by any cluster structure present, and rapidly decomposes a graph into cohesive clusters. The potential of the GeneMCL algorithm is demonstrated with a 5,730 gene subset (IGS) of the Van't Veer breast cancer database, for which the clusterings are shown to reflect underlying biological mechanisms.     

Kinetic study of angiotensin converting enzyme activity by capillary electrophoresis after in-line reaction at the capillary inlet

The in-capillary reaction of angiotensin converting enzyme (ACE) with the tripeptide substrate hippuryl-L-histidyl-L-leucine was studied. ACE activity was determined by the quantitation of the product, hippuric acid, at 230 nm. Reaction occurred at the capillary inlet during a predetermined waiting period, followed by the electrophoretic separation of the compounds. When the set-up was reversed, i.e. reaction at the opposite side after short-end injection of enzyme and substrate, separation was achieved in less than 5 min. Using the Lineweaver-Burk equation, an average Michaelis constant for ACE from rabbit lung was calculated to be 1.16 +/- 0.12 mM, a value consistent with previously reported data.     

High-resolution laser ablation-inductively coupled plasma-mass spectrometry imaging of cisplatin-induced nephrotoxic side effects

Two-dimensional elemental mapping (bioimaging) via laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was performed on 5 μm thick formalin-fixed, paraffin-embedded kidney tissue sections from Cynomolgus monkeys administered with increasing pharmacological doses of cisplatin. Laterally resolved pixels of 1 μm were achieved, enabling elemental analysis on a (sub-)cellular level. Zones of high Pt response were observed in the renal cortex, where proximal tubules are present, the epithelium of which is responsible for partial reabsorption of cisplatin. Histopathological evaluation, of hematoxylin and eosin-stained serial sections, adjacent to the sections probed via LA-ICP-MS, revealed minimal to mild cisplatin-related lesions (<100 μm) in the renal cortex. Necrotic proximal tubules with sloughed epithelial cells in their lumen could be linked directly to the areas with the highest accumulation of cisplatin, indicating a direct link between cellular concentration and toxicity, thereby providing more insight into the mechanisms through which renal damage occurs.     

Synthesis and metal complexation studies of [2n]thiacalix[m]arene[m]pyrazine

Novel [2_n]thiacalixarenepyrazine and [2_n]thiacalixarenetriazine systems were synthesised by one-pot S_NAr reactions. A screening of the metal-complexing ability of [2₆]hexathiacalix[3]arene[3]pyrazine revealed its affinity for Cu^I, Cu^II and Ag^I metal salts.     

Molecular Fluorescence Imaging Spectroscopy for Mapping Low Concentrations of Red Lake Pigments: Van Gogh's Painting The Olive Orchard

Vincent van Gogh used fugitive red lake pigments that have faded in some paintings. Mapping their distribution is key to understanding how his paintings have changed with time. While red lake pigments can be identified from microsamples, in situ identification and mapping remain challenging. This paper explores the ability of molecular fluorescence imaging spectroscopy to identify and, more importantly, map residual non‐degraded red lakes. The high sensitivity of this method enabled identification of the emission spectra of eosin (tetrabromine fluorescein) lake mixed with lead or zinc white at lower concentrations than elemental X‐ray fluorescence (XRF) spectroscopy used on account of bromine. The molecular fluorescence mapping of residual eosin and two carmine red lakes in van Gogh's The Olive Orchard is demonstrated and compared with XRF imaging spectroscopy. The red lakes are consistent with the composition of paint tubes known to have been used by van Gogh.     

On the Validity of Entropy Production Principles for Linear Electrical Circuits

We explain the (non-)validity of close-to-equilibrium entropy production principles in the context of linear electrical circuits. Both the minimum and the maximum entropy production principles are understood within dynamical fluctuation theory. The starting point are Langevin equations obtained by combining Kirchoff’s laws with a Johnson-Nyquist noise at each dissipative element in the circuit. The main observation is that the fluctuation functional for time averages, that can be read off from the path-space action, is in first order around equilibrium given by an entropy production rate. That allows to understand beyond the schemes of irreversible thermodynamics (1) the validity of the least dissipation, the minimum entropy production, and the maximum entropy production principles close to equilibrium; (2) the role of the observables’ parity under time-reversal and, in particular, the origin of Landauer’s counterexample (1975) from the fact that the fluctuating observable there is odd under time-reversal; (3) the critical remark of Jaynes (1980) concerning the apparent inappropriateness of entropy production principles in temperature-inhomogeneous circuits.     

Proactive heuristic procedures for robust project scheduling: An experimental analysis

Solution-robust project scheduling is a growing research field aiming at constructing proactive schedules to cope with multiple disruptions during project execution. When stochastic activity durations are considered, including time buffers between activities is a proven method to improve the stability of a baseline schedule.     

Schottky Mass Measurements of Cooled Exotic Nuclei

Projectile fragments of a ²⁰⁹Bi beam were separated in flight with the fragment separator FRS and injected into the experimental storage ring ESR. In the ESR a beam containing up to about 100 different isotopes was cooled to a relative velocity spread of δv/v=10⁻⁶ by means of the electron cooler. The image currents of the ions induced in a Schottky pick-up probe at each turn were recorded. A subsequent Fast Fourier Transformation of these signals yields the revolution frequencies of the different isotopes stored in the ESR. Unknown masses of more than 150 neutron-deficient nuclides in the element range of 52≤Z≤85 have been measured directly by Schottky Mass Spectrometry and in addition more than 60 new masses have been obtained from α-decay chains. These new mass data allow the location of the one-proton dripline and the prediction of the two-proton dripline for heavy nuclides. The experimental masses are compared with different theoretical predictions. This revised version was published online in July 2006 with corrections to the Cover Date.     

Sensitive laserspectroscopy on ions with hyperfine split transitions

Collinear laser—fast alkaline-earth ion beam interaction can be monitored sensitively by a detection sequence consisting of optical pumping to a metastable state, state-dependent neutralization, and separate counting of ions and atoms. Deceleration of the ions prior to neutralization strongly increases the sensitivity of the method. For ions with hyperfine split transitions the sensitivity can be considerably improved by a two-step optical pumping sequence. In this contribution, the results of rate equation calculations are compared to experimental results for Ba-and Sr-beams, including a shortlived⁹⁹Sr beam of very low intensity.