Hemithio-analogues of meisenheimer complexes and sulphide group activation of aromatic substitution by alkoxides

EtO^? in DMSO adds to ethylthiopicrate at C-3 to generate an ephemeral

-adduct which ends into 1-ethylthio-4-ethoxy-2,5-dinitrobenzene, whilst ethyl picrate gives two adducts of attack of EtS^? at C-3 or C-1.     

Recovering Beam Search: Enhancing the Beam Search Approach for Combinatorial Optimization Problems

A hybrid heuristic method for combinatorial optimization problems is proposed that combines different classical techniques such as tree search procedures, bounding schemes and local search. The proposed method enhances the classic beam search approach by applying to each partial solution corresponding to a node selected by the beam, a further test that checks whether the current partial solution is dominated by another partial solution at the same level of the search tree. If this is the case, the latter solution becomes the new current partial solution. This step allows to partially recover from previous wrong decisions of the beam search procedure and can be seen as a local search step on the partial solution. We present here the application to two well known combinatorial optimization problems: the two-machine total completion time flow shop scheduling problem and the uncapacitated p-median location problem. In both cases the method strongly improves the performances with respect to the basic beam search approach and is competitive with the state of the art heuristics.     

Combining Swaps and Node Weights in an Adaptive Greedy Approach for the Maximum Clique Problem

In this work, the NP-hard maximum clique problem on graphs is considered. Starting from basic greedy heuristics, modifications and improvements are proposed and combined in a two-phase heuristic procedure. In the first phase an improved greedy procedure is applied starting from each node of the graph; on the basis of the results of this phase a reduced subset of nodes is selected and an adaptive greedy algorithm is repeatedly started to build cliques around such nodes. In each restart the selection of nodes is biased by the maximal clique generated in the previous execution. Computational results are reported on the DIMACS benchmarks suite. Remarkably, the two-phase procedure successfully solves the difficult Brockington-Culberson instances, and is generally competitive with state-of-the-art much more complex heuristics.     

Weighted approximation of functions on the real line by Bernstein polynomials

The authors give error estimates, a Voronovskaya-type relation, strong converse results and saturation for the weighted approximation of functions on the real line with Freud weights by Bernstein-type operators.     

Synthesis,spectroscopic characterization (IR, 1H, 13C and 119Sn NMR,electrospray mass spectrometry) and toxicity of new organotin(IV) complexes with N,N′,O‐ and N,N′,S‐scorpionate ligands

New organotin(IV) derivatives containing the anionic ligands bis(3,5‐dimethylpyrazol‐1‐yl)dithioacetate [LCS₂]⁻ and bis(3,5‐dimethylpyrazol‐1‐yl)acetate [LCO₂]⁻ have been synthesized from reaction between (CH₃)₂SnCl₂ and lithium salts of the ligands. Mononuclear complexes of the type {[LCX₂](CH₃)₂SnCl} (X = S or O) have been obtained and fully characterized by elemental analyses and FT‐IR in the solid state and by NMR (¹H, ¹³C and ¹¹⁹Sn) spectroscopy, conductivity measurements and electrospray ionization mass spectrometry in solution. The acute toxicity of new organotin(IV) derivatives on rat was studied, comparing their effect with those of dimethyltin chloride (CH₃)₂SnCl₂. The comparison of LD₅₀ of organotin(IV) complexes and (CH₃)₂SnCl₂ administered intraperitoneally, as a single dose, evaluated in vivo on rats, showed that toxicity decreases as follows: (CH₃)₂SnCl₂ > LCO₂ > LCS₂. The effect of these organotin(IV) complexes on DNA was evaluated in vitro and in vivo on rats treated with different doses of these compounds (1/20 LD₅₀ and 1/100 LD₅₀). The lymphocyte DNA status was assessed by the comet assay, a rapid and sensitive single‐cell electrophoresis technique, used to detect primary DNA damage in individual cells. After 36 h from the start of treatment the two new organotin(IV) derivatives induced a significant rise in comet assay parameters, indicating an increasing presence of damaged DNA. Copyright © 2005 John Wiley & Sons, Ltd.     

Use of isothermal microcalorimetry data for the determination of integral molar entropies of adsorption at the gas—solid interface by a quasi-equilibrium procedure

The aim of this paper is to describe the present position in the experimental determination of entropies of adsorption. After pointing out the limitations of the “isosteric” approach and after stressing the fact that the most interesting entropy to know is the integral molar entropy of adsorption, the authors show how the use of isothermal adsorption microcalorimetry, with a special quasi-reversible procedure, allows this entropy to be determined satisfactorily from the thermodynamic point of view.     

Study of double pomeron exchange in pp collisions at √s=31GeV

The reaction pp→ppπ⁺π^? at √s=31GeV was studied at the Split Field Magnet Facility of the CERN-ISR. Selecting events with two leading protons of x>0.9 and a rapidity gap Δy>2 between the protons and both pions a sample of 720 events is obtained representing a cross section of 25±10μb. The mass distribution of the dipion system, x and p_T distributions for the protons are presented and analyzed for the presence of double pomeron exchange.     

The photoelectron spectrum and molecular geometry of bicyclo[2.1.1]hexane

The He(I) photoelectron spectrum of bicyclo[2.1.1]hexane shows excellent correlation with a theoretical spectrum based on the eigenvalues obtained in an ab initio calculation at the theoretical molecular geometry. By contrast, a calculation performed at the experimental geometry exhibits an effect of enhanced ring strain in showing a first ionization energy which is considerably lower than the experimental value. This observation offers experimental support for the recent claim that the published structure for bicyclo [2.1.1]hexane based on electron-diffraction measurements is incorrect. It also accounts for inconsistencies observed in the calculated values of some spin—spin coupling constants for substituted bicyclo[2.1.1]hexanes.     

Comparison between experimental decay of the compound nuclei150Gd and evaporation calculations

The deexcitation of the compound nucleus¹⁵⁰Gd formed by¹⁵⁶O+¹³⁴Ba and⁴⁰Ar+¹¹⁰Pd have been studied. Excitation functions were determined for various exit channels: (HI, × n) withx=3, 4, 5 (HI, pxn) withx=2, 3, 4 (HI, axn) withx=3 and 5. A systematic comparison has been made between these experimental data and the results of evaporation calculation using the ALI CE code. The very good agreement obtained for the total residue cross section disappears completely when a more detailed analysis of the different contributions is performed. Absolute and relative cross sections are not reproduced; excitation functions of each individual channel (HI, 3n), (HI, 4n) etc. ... are not found at the right place in energy. A very preliminary explanation for such a shift towards higher energies is suggested.