The mechanism of the elimination kinetics of 2-bromo-2-butene in the gas phase

The kinetics of the gas phase elimination of 2-bromo-2-butene were determined in a static system over the temperature range of 340–380°C and pressure range of 37–134 torr. The reaction in seasoned vessels, even in the presence of a free radical inhibitor, is catalyzed by hydrogen bromide. Under maximum catalysis of HBr, the kinetics were found to be of order 1.0. The reaction, when maximally catalyzed with HBr, appears to undergo a molecular elimination of HBr which follows first-order kinetics. The products are 1,2-butadiene and hydrogen bromide. The rate coefficients. under maximum catalysis, are given by the Arrhenius equation log ??₁(s^?1) = (13.57 ± 0.56) ? (200.4 ± 6.8) kJ mol^?1 (2.303RT)^?1. The catalyzed pyrolysis of 2-bromo-2-butene appears to proceed through a six-membered cyclic transition-state type of mechanism.     

A matricial extension of the Helson-Sarason theorem and a characterization of some multivariate linearly completely regular processes

We generalize the theorems of Helson-Szegö and Helson-Sarason for matricial measures. We study two-weighted inequalities for the Hilbert transform in [0, 2π] and in R and give a characterization for the positivity of the angle between past and future of multivariate weakly stationary stochastic processes, in the discrete and the continuous case. We also characterize the multivariate weakly stationary stochastic processes that are linearly completely regular and study the rate of convergence of the maximal correlation coefficient.     

State‐of‐the‐art all‐silicon sub‐bandgap photodetectors at telecom and datacom wavelengths

Silicon‐based technologies provide an ideal platform for the monolithic integration of photonics and microelectronics. In this context, a variety of passive and active silicon photonic devices have been developed to operate at telecom and datacom wavelengths, at which silicon has minimal optical absorption ‐ due to its bandgap of 1.12 eV. Although in principle this transparency window limits the use of silicon for optical detection at wavelengths above 1.1 μm, in recent years tremendous advances have been made in the field of all‐silicon sub‐bandgap photodetectors at telecom and datacom wavelengths. By taking advantage of emerging materials and novel structures, these devices are becoming competitive with the more well‐established technologies, and are opening new and intriguing perspectives. In this paper, a review of the state‐of‐the‐art is presented. Devices based on defect‐mediated absorption, two‐photon absorption and the internal photoemission effect are reported, their working principles are elucidated and their performance discussed and compared.

     

Aryl-aryl bond formation by the fluoride-free cross-coupling of aryldisiloxanes with aryl bromides

The prevalence of the biaryl structural motif in biologically interesting and synthetically important molecules has inspired considerable interest in the development of methods for aryl-aryl bond formation. Herein we describe a novel strategy for this process involving the fluoride-free, palladium-catalysed cross-coupling of readily accessible aryldisiloxanes and aryl bromides. Using a statistical-based optimisation process, preparatively useful reaction conditions were formulated to allow the cross-coupling of a wide range of different substrates. This methodology represents an attractive, cost-efficient, flexible and robust alternative to the traditional transition-metal-catalysed routes typically used to generate molecules containing the privileged biaryl scaffold.     

Photochemically initiated oxidative carbon-carbon bond-cleavage reactivity in chlorodiketonate Ni(II) complexes

Three mononuclear Ni(II) complexes containing a 2-chloro-1,3-diketonate ligand and supported by the 6-Ph(2)TPA chelate, as well as analogues that lack the 2-chloro substituent on the β-diketonate ligand, have been prepared and characterized. Upon irradiation at 350 nm under aerobic conditions, complexes containing the 2-chloro-substituted ligands undergo reactions to generate products resulting from oxidative cleavage, α-cleavage, and radical-derived reactions involving the 2-chloro-1,3-diketonate ligand. Mechanistic studies suggest that the oxidative cleavage reactivity, which leads to the production of carboxylic acids, is a result of the formation of superoxide, which occurs through reaction of reduced nickel complexes with O(2). The presence of the 2-chloro substituent was found to be a prerequisite for oxidative carbon-carbon bond-cleavage reactivity, as complexes lacking this functional group did not undergo these reactions following prolonged irradiation. The approach toward investigating the oxidative reactivity of metal β-diketonate species outlined herein has yielded results of relevance to the proposed mechanistic pathways of metalloenzyme-catalyzed β-diketonate oxidative cleavage reactions.     

Nonlinear optics in spheres: from second harmonic scattering to quasi‐phase matched generation in whispering gallery modes

Over the last fifteen years, a series of theoretical and experimental investigations have demonstrated the usefulness of circular geometries to tailor second‐order nonlinear optical effects. However, until recently, such effects have remained rather weak, calling for their enhancement. In parallel, developments in the field of high quality factor spherical or ring resonators have shown that many different types of light‐matter interactions can be dramatically amplified when light is coupled in the whispering gallery modes of such resonators. In high‐quality spherical micro‐resonators, close to one million interactions can occur between a nonlinear molecule and a circulating light pulse. Recent research on nonlinear optics in spherical geometry is reviewed, from micrometer‐size spheres to whispering gallery mode resonators.     

A primal-dual interior-point algorithm for quadratic programming

In this paper we propose a primal-dual interior-point method for large, sparse, quadratic programming problems. The method is based on a reduction presented by Gonzalez-Lima, Wei, and Wolkowicz [14] in order to solve the linear systems arising in the primal-dual methods for linear programming. The main features of this reduction is that it is well defined at the solution set and it preserves sparsity. These properties add robustness and stability to the algorithm and very accurate solutions can be obtained. We describe the method and we consider different reductions using the same framework. We discuss the relationship of our proposals and the one used in the LOQO code. We compare and study the different approaches by performing numerical experimentation using problems from the Maros and Meszaros collection. We also include a brief discussion on the meaning and effect of ill-conditioning when solving linear systems.This work was partially supported by DID-USB (GID-001).     

The gas-phase elimination kinetics of 3-buten-1-methanesulphonate and 3-methyl-3-buten-1-methanesulphonate

The elimination kinetics of the title compounds were carried out in a static system over the temperature range of 290–330°C and pressure range of 29.5–124 torr. The reactions, carried out in seasoned vessels with allyl bromide, obey first-order rate law, are homogeneous and unimolecular. The temperature dependence of the rate coefficients is given by the following Arrhenius equations: for 3-buten-1-methanesulphonate, log k₁(s^?1) = (12.95 ± 0.53) ? (175.3 ± 5.9)kJ mol^?1(2.303RT)^?1; and for 3-methyl-3-buten-1-methanesulphonate, log k₁(s^?1) = (12.98 ± 0.40) ? (174.7 ± 4.5)kJ mol^?1(2.303RT)^?1. The olefinic double bond appears to assist in the rate of pyrolysis. The mechanism is described in terms of an intimate ion-pair intermediate. © 1995 John Wiley & Sons, Inc.