Reactions of a Transient Carbonyl(chloro)(hydrido)ruthenium(II) Complex with Ethylene,Alkynes, and CO; Chemistry of the New Anion [Ru2(CO)4Cl5]−

A 97% yield of [Ru ₃ (CO) ₁₂ ] (2) in 20 minutes is obtained simply by treating [Ru(CO)₃Cl₂(thf)] with KOH under CO (1 atm). The reduction to Ru⁰ can be explained in terms of the facile reductive elimination of HCl from the transient hydrido complex 1 . Though elusive, the latter can be intercepted by olefins or alkynes to produce trappable alkyl or alkenyl complexes such as 3 and 4 .█ denotes a vacant coordination site.     

Self-absorption effects in radially and axially viewed inductively coupled plasma-atomic emission spectrometry – the key role of the operating conditions

Self-absorption effects leading to curvatures of the upper part of calibration graphs were investigated in multichannel detection ICP–AES. A dual view Optima 3000 ICP system was used to enable the simultaneous determination of 38 lines for both radial and axial viewing. Resonance and non-resonance lines were selected for both atomic and ionic lines. The concentrations of 22 standards were in the range 0.1–100 mg L^–1 and two sets of operating conditions, namely power and carrier gas flow rate, were used to evaluate their influence. It was found that these two conditions, and in particular the carrier gas flow rate, play a major role in self-absorption effects. Except for strongly absorbing lines, it was possible, under suitable conditions, to reduce or to suppress differences between self-absorption effects in radial and axial viewing, enabling extension of the range of linearity of axial viewing to higher concentrations. A diagnostic tool, based on emission line ratios, is proposed for detection of self-absorption. A calibration procedure is given for strongly absorbing lines affected by self-absorption even when operating conditions were optimized.     

Variable space search for graph coloring

Let G=(V,E) be a graph with vertex set V and edge set E. The k-coloring problem is to assign a color (a number chosen in {1,…,k}) to each vertex of G so that no edge has both endpoints with the same color. We propose a new local search methodology, called Variable Space Search, which we apply to the k-coloring problem. The main idea is to consider several search spaces, with various neighborhoods and objective functions, and to move from one to another when the search is blocked at a local optimum in a given search space. The k-coloring problem is thus solved by combining different formulations of the problem which are not equivalent, in the sense that some constraints are possibly relaxed in one search space and always satisfied in another. We show that the proposed algorithm improves on every local search used independently (i.e., with a unique search space), and is competitive with the currently best coloring methods, which are complex hybrid evolutionary algorithms.     

Comparison of agent-based scheduling to look-ahead heuristics for real-time transportation problems

We consider the real-time scheduling of full truckload transportation orders with time windows that arrive during schedule execution. Because a fast scheduling method is required, look-ahead heuristics are traditionally used to solve these kinds of problems. As an alternative, we introduce an agent-based approach where intelligent vehicle agents schedule their own routes. They interact with job agents, who strive for minimum transportation costs, using a Vickrey auction for each incoming order. This approach offers several advantages: it is fast, requires relatively little information and facilitates easy schedule adjustments in reaction to information updates. We compare the agent-based approach to more traditional hierarchical heuristics in an extensive simulation experiment. We find that a properly designed multi-agent approach performs as good as or even better than traditional methods. Particularly, the multi-agent approach yields less empty miles and a more stable service level.     

Highly cooperative formation of bis-urea based supramolecular polymers

Eleven bis-ureas have been synthesized, and some of their properties are reported. Several of these compounds form supramolecular polymers in organic solvents. The self-association is shown by FTIR spectroscopy to display cooperativity at two levels. The first level of cooperativity is due to the synergistic association of the two urea functions of a single molecule. The second level of cooperativity is revealed by the fact that the formation of dimers is less favored than that of long oligomers.     

Droplet traffic at a simple junction at low capillary numbers

We report that, when a train of confined droplets flowing through a channel reaches a junction, the droplets either are alternately distributed between the different outlets or all collect into the shortest one. We argue that this behavior is due to the hydrodynamic feedback of droplets in the different outlets on the selection process occurring at the junction. A "mean field" model, yielding semiquantitative results, offers a first guide to predict droplet traffic in branched networks.     

Raman modes of index-identified freestanding single-walled carbon nanotubes

Using electron diffraction on freestanding single-walled carbon nanotubes, we have determined the structural indices (n,m) of tubes in the diameter range from 1.4 to 3 nm. On the same freestanding tubes, we have recorded Raman spectra of the tangential modes and the radial breathing mode. For the smaller diameters (1.4-1.7 nm), these measurements confirm previously established radial breathing mode frequency versus diameter relations and would be consistent with the theoretically predicted proportionality to the inverse diameter. However, for extending the relation to larger diameters, either a yet unexplained environmental constant has to be assumed, or the linear relation has to be abandoned.