Rate coefficients for the reaction of OH with Cl2, Br2, and I2 from 235 to 354 K

Rate coefficients for the reaction of OH with Cl₂, (k₁), Br₂, (k₂) and I₂, (k₃), were measured under pseudo‐first‐order conditions in OH. OH was produced by pulsed laser photolysis of H₂O₂ (or HNO₃) and its temporal profile was monitored by laser‐induced fluorescence. The measured rate coefficients for k₁ (231–354 K) and k₂ (235–357 K) are: k₁ (T) = (3.77 ± 1.02) × 10⁻¹² exp[−(1228 ± 140)/T] cm³ molecule⁻¹ s⁻¹ k₂ (T) = (1.98 ± 0.51) × 10⁻¹¹ exp[(238 ± 70)/T] cm³ molecule⁻¹ s⁻¹ k₃ was independent of temperature between 240 and 348 K with an average value of (2.10 ± 0.60) × 10⁻¹⁰ cm³ molecule⁻¹ s⁻¹. The quoted uncertainties are 2σ (95% confidence limits, 1σ_A = Aσ_lnA) and include estimated systematic errors. Our measurements significantly im‐prove the accuracy of k₁. This is the first report of a slight negative temperature dependence for k₂ and of the temperature independence of k₃. © 1999 John Wiley & Sons, Inc.* Int J Chem Kinet 31: 417–424, 1999     

The “progressive mixture” estimator for regression trees

We present a version of O. Catoni's “progressive mixture estimator” (1999) suited for a general regression framework. Following basically Catoni's steps, we derive strong non-asymptotic upper bounds for the Kullback–Leibler risk in this framework. We give a more explicit form for this bound when the models considered are regression trees, present a modified version of the estimator in an extended framework and propose an approximate computation using a Metropolis algorithm.     

Kinetics of the reactions of CH3O with Cl and CIO

The kinetics of the reactions CH₃O + Cl → H₂CO + HCl (1) and CH₃O + ClO → H₂CO + HOCl (2) have been studied using the discharge-flow techniques. CH₃O was monitored by laser-induced fluorescence, whereas mass spectrometry was used for the detection or titration of other species. The rate constants obtained at 298 K are: k₁ = (1.9 ± 0.4) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹ and k₂ = (2.3 ± 0.3) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹. These data are useful to interpret the results of the studies of the reactions of CH₃O₂ with Cl and ClO which, at least partly, produce CH₃O radicals. © 1996 John Wiley & Sons, Inc.     

Enzyme-catalyzed syntheses of poly(1,6-hexanediyl maleate) and poly(1,6-hexanediyl fumarate) in organic medium

The lipase-catalyzed preparation of poly(1,6-hexanediyl maleate) by transesterification of 1,6-hexanediol and dimethyl maleate is described. A configurationally pure poly(1,6-hexanediyl maleate) exhibiting exclusively cis structure was obtained. During the reaction, a substantial amount of macrolactones was formed. They were isolated, and the cyclic oligomer with y = 2 was found to predominate. Cycles are semi-crystalline, while no melting point was detected for the linear poly(1,6-hexanediyl maleate). We assume that the linear unsaturated polyester is completely amorphous owing to its cis configuration.     

A branch and cut algorithm for nonconvex quadratically constrained quadratic programming

We present a branch and cut algorithm that yields in finite time, a globally ε-optimal solution (with respect to feasibility and optimality) of the nonconvex quadratically constrained quadratic programming problem. The idea is to estimate all quadratic terms by successive linearizations within a branching tree using Reformulation-Linearization Techniques (RLT). To do so, four classes of linearizations (cuts), depending on one to three parameters, are detailed. For each class, we show how to select the best member with respect to a precise criterion. The cuts introduced at any node of the tree are valid in the whole tree, and not only within the subtree rooted at that node. In order to enhance the computational speed, the structure created at any node of the tree is flexible enough to be used at other nodes. Computational results are reported that include standard test problems taken from the literature. Some of these problems are solved for the first time with a proof of global optimality. Received December 19, 1997 / Revised version received July 26, 1999?Published online November 9, 1999     

Reactivity of 4‐chlorobenzo[c][2,7]naphthyridines towards Pd(0) catalyzed coupling reactions and nucleophilic substitutions. aroylation by nucleophilic substitution with analogues of acyl anions

Various 4‐substituted benzo[c][2,7]naphthyridines were prepared from the corresponding 4‐chloro derivative by Pd(0) coupling reaction or nucleophilic substitution. More particularly, 4‐aroyl‐benzo[e][2,7]naph‐thyridines were synthesized by aroylation with arenecarbaldehydes in the presence of 1,3‐dimethylimida‐zolium iodide.     

A Constraint Programming Framework for Local Search Methods

We propose in this paper a novel integration of local search algorithms within a constraint programming framework for combinatorial optimization problems, in an attempt to gain both the efficiency of local search methods and the flexibility of constraint programming while maintaining a clear separation between the constraints of the problem and the actual search procedure. Each neighborhood exploration is performed by branch-and-bound search, whose potential pruning capabilities open the door to more elaborate local moves, which could lead to even better approximate results. Two illustrations of this framework are provided, including computational results for the traveling salesman problem with time windows. These results indicate that it is one order of magnitude faster than the customary constraint programming approach to local search and that it is competitive with a specialized local search algorithm.