Synchrotron photoionization measurements of OH-initiated cyclohexene oxidation: ring-preserving products in OH + cyclohexene and hydroxycyclohexyl + O2 reactions

Earlier synchrotron photoionization mass spectrometry experiments suggested a prominent ring-opening channel in the OH-initiated oxidation of cyclohexene, based on comparison of product photoionization spectra with calculated spectra of possible isomers. The present work re-examines the OH + cyclohexene reaction, measuring the isomeric products of OH-initiated oxidation of partially and fully deuterated cyclohexene. In particular, the directly measured photoionization spectrum of 2-cyclohexen-1-ol differs substantially from the previously calculated Franck-Condon envelope, and the product spectrum can be fit with no contribution from ring-opening. Measurements of H(2)O(2) photolysis in the presence of C(6)D(10) establish that the addition-elimination product incorporates the hydrogen atom from the hydroxyl radical reactant and loses a hydrogen (a D atom in this case) from the ring. Investigation of OH + cyclohexene-4,4,5,5-d(4) confirms this result and allows mass discrimination of different abstraction pathways. Products of 2-hydroxycyclohexyl-d(10) reaction with O(2) are observed upon adding a large excess of O(2) to the OH + C(6)D(10) system.     

Insights into the pathophysiology of the antiphospholipid syndrome provided by atomic force microscopy

The antiphospholipid syndrome (APS) is an enigmatic autoimmune disorder in which patients present with thrombosis and/or recurrent pregnancy losses together with laboratory evidence for the presence of autoantibodies in the blood that recognize proteins that bind to anionic phospholipids - the most important of which is β(2)-glycoprotein I (β(2)GPI). Earlier, we hypothesized that the clinical manifestations arise from antibody-induced disruption of a two-dimensional anticoagulant crystal shield, composed of annexin A5, present on placental trophoblast plasma membranes. Accordingly, we reasoned that a high resolution imaging technology, such as atomic force microscopy could be used to investigate such molecular interactions at high resolution in a non-fixed hydrated environment. This review will focus on the contribution of this technique to the elucidation of the mechanism of APS.     

The reaction of hydroxyethyl radicals with O2: A theoretical analysis and experimental product study

Reactions of α-hydroxyethyl (CH₃CHOH) and β-hydroxyethyl (CH₂CH₂OH) radicals with oxygen are of key importance in ethanol combustion. High-level ab initio calculations of the potential energy surfaces of these two reactions were coupled with master equation methods to compute rate coefficients and product branching ratios for temperatures of 250-1000 K. The α-hydroxyethyl + O₂ reaction is controlled by the barrierless entrance channel and shows negligible pressure dependence; in contrast, the reaction of the β isomer displays pronounced pressure dependence. The high pressure limit rate coefficients of both reactions are about the same at the temperatures investigated. Products of the reactions were monitored experimentally at 4 Torr and 300-600 K using tunable synchrotron photoionization mass spectrometry. Hydroxyethyl radicals were produced from the reaction of ethanol with chlorine atoms and the β isomer was also selectively produced by the addition reaction C₂H₄ + OH → CH₂CH₂OH. Formaldehyde, acetaldehyde, vinyl alcohol and H₂O₂ products were detected, in qualitative agreement with the theoretical predictions.     

Augmented non-quadratic penalty algorithms

Auslender, Cominetti and Haddou have studied, in the convex case, a new family of penalty/barrier functions. In this paper, we analyze the asymptotic behavior of augmented penalty algorithms using those penalty functions under the usual second order sufficient optimality conditions, and present order of convergence results (superlinear convergence with order of convergence 4/3). Those results are related to the analysis of pure penalty algorithms, as well as augmented penalty using a quadratic penalty function. Limited numerical examples are presented to appreciate the practical impact of this local asymptotic analysis.This research was partially supported by NSERC grant OGP0005491     

Bicomplex Quantum Mechanics: I. The Generalized Schrödinger Equation

We introduce the set of bicomplex numbers which is a commutative ring with zero divisors defined by where We present the conjugates and the moduli associated with the bicomplex numbers. Then we study the bicomplex Schr?dinger equation and found the continuity equations. The discrete symmetries of the system of equations describing the bicomplex Schr?dinger equation are obtained. Finally, we study the bicomplex Born formulas under the discrete symmetries. We obtain the standard Born’s formula for the class of bicomplex wave functions having a null hyperbolic angle.     

PARALLEL AUXILIARY SPACE AMG FOR H（curl） PROBLEMS

In this paper we review a number of auxiliary space based preconditioners for the second order definite and semi-definite Maxwell problems discretized with the lowest order Nedelec finite elements. We discuss the parallel implementation of the most promising of these methods, the ones derived from the recent Hiptmair-Xu （HX） auxiliary space decomposition [Hiptmair and Xu, SIAM J. Numer. Anal., 45 （2007）, pp. 2483-2509]. An extensive set of numerical experiments demonstrate the scalability of our implementation on large-scale H（curl） problems.     

算术级数中的陈景润定理 *

设N为一充分大的偶数且q≥ 1 ,(l_i,q) =1 (i=1 ,2 ) ,l₁+l₂ ≡N(modq) .证明了方程N =p+P₂ ,p≡l1(modq) ,P₂ ≡l₂ (modq)对区间 1 ,N^1/37中除了ON^1/37log^-5 N个例外的整数q ,都有无穷多解 ,其中p是素数 ,P₂ 为一至多有2个素因子的殆素数 .     

多尺度B样条小波边缘检测算子

基于B样条理论提出了一类新的多尺度小波变换,通过其零交叉或模极值能有效地表示和检测信号或图象的边缘,对任意n次B样条,导出了相应的分解和重建的快速算法,对应的用于分解和重建的滤波器的时域和频域响应也被精确地给出.从时频局部化的角度对不同次数的B样条作了分析,认为3次B样条小波在边缘提取等实际应用中是渐近最优的,结果也为B样条小波在立体视觉匹配、滤噪等方面的进一步应用提供了基础.     

“下愚”最智 “上智”最愚

历代反动派总是宣扬孔老二“上智与下愚不移”的唯心论说教,把它作为“剥削有理”、“压迫有理”的根据。林彪这个地主资产阶级的代理人,为了篡党夺权,复辟资本主义,建立林家法西斯王朝,也鼓吹“上智下愚”的谬论。他把自己吹成“生而知之”的“天才”,以“至贵”、超人自居,污蔑劳动人民“愚昧”、“落后”,只会说“恭喜发财”,只能想“油盐酱醋柴”。     

Direct observation of the gas-phase Criegee intermediate (CH2OO)

Carbonyl oxide species play a key role in tropospheric oxidation of organic molecules and in low-temperature combustion processes. In the late 1940s, Criegee first postulated the participation of carbonyl oxides, now often called "Criegee intermediates," in ozonolysis of alkenes. However, despite decades of effort, no gas phase Criegee intermediate has before been observed. As a result, knowledge of gas phase carbonyl oxide reactions has heretofore been inferred by indirect means, with derived rate coefficients spanning orders of magnitude. We have directly detected the primary Criegee intermediate, formaldehyde oxide (CH2OO), in the chlorine-initiated gas-phase oxidation of dimethyl sulfoxide (DMSO). This work not only establishes that the Criegee intermediate is formed in DMSO oxidation also but opens the possibility for explicit kinetics studies on this critical atmospheric species.