HO2 ELIMINATION FROM α-HYDROXYALKYLPEROXYL RADICALS IN AQUEOUS SOLUTION

Abstract— In aqueous solutions α-hydroxyalkylperoxyl radicals undergo a spontaneous and a base catalysed HO₂ elimination. From kinetic deuterium isotope effects, temperature dependence, and the influence of solvent polarity it was concluded that the spontaneous reaction occurs via an HO₂ elimination followed by the dissociation of the latter into H⁺ and O₂^-. The rate constant of the spontaneous HO₂ elimination increases with increasing methyl substitution in α-position ( k (CH₂(OH)O₂) < 10s^-1 k (CH₃CH(OH)O₂) = 52s^-1 k ((CH₃)₂C(OH)O₂) = 665 s^-1). The OH^- catalysed reaction is somewhat below diffusion controlled. The mixture of peroxyl radicals derived from polyhydric alcohols eliminate HO₂ at two different rates. Possible reasons for this behaviour are discussed. The mixture of the six peroxyl radicals derived from d -glucose are observed to eliminate HO₂ with at least three different rates. The fastest rate is attributed to the HO₂ elimination from the peroxyl radical at C-l ( k > 7000s^-1). Because of the HO₂ eliminations the peroxyl radicals derived from d -glucose do not undergo a chain reaction in contrast to peroxyl radicals not containing an α-OH group. In competition with the first order elimination reactions the α-hydroxylalkylperoxyl radicals undergo a bimolecular decay. These reactions are briefly discussed.     

Synchronization of the chaotic secure communication system with output state delay

In this paper, we utilize a proper Lyapunov function and Lyapunov theorem, combined with LMIs method, in order to design a controller L, which ensures the synchronization between the transmission and the reception ends of the chaotic secure communication system with time-delay of output state. Meanwhile, for the purpose of increasing communication security, we encrypt and decrypt the original to-be-transmitted message with the techniques of n-shift cipher and public key. The result of simulation shows that the proposed method is able to synchronize the transmission and the reception ends of the system, and moreover, to recover the original message at the reception end. Therefore, the method proposed in this paper is effective and feasible to apply in the chaotic secure communication system.     

Expeditious Synthesis of Enantiopure,Orthogonally Protected Bis‐α‐Amino Acids (OPBAAs) and their Use in a Study of Nod1 Stimulation

A convenient approach towards the synthesis of orthogonally protected chiral bis‐α‐amino acids (OPBAAs) is described. The key transformations include: (1) a highly stereoselective conjugation (alkylation) of the Schöllkopf bis‐lactim ethers and oxazolidinyl alkyl halides to build a backbone skeleton; and (2) our orthogonal protection strategy. A series of enantiopure OPBAAs bearing a variety of alkyl chain as a spacer; two stereogenic centers; and three protecting groups were prepared as examples. These versatile molecules were applied to the synthesis of biologically interesting di‐ or tri‐peptide analogues, including chiral iE‐meso‐DAP and A‐iE‐meso‐DAP, for the study of Nod1 activation in the innate immune response.     

Convex curves moving translationally in the plane

We show that a nontrivial homothetic self-similar solution can happen only when F(k)=kα or F(k)=−k−α. We also derive a parametric representation of a translational self-similar solution. A translational self-similar solution may have self-intersections but cannot be a simple closed curve for any F(k).     

A fast Godunov method for the water‐hammer problem

An efficient Godunov‐type numerical method with second‐order accuracy was developed to simulate the water‐hammer problem in piping. The exact solutions of the Riemann problem were analysed and illustrated on the intriguing solution diagram by properly introducing dimensionless variables within reasonably practical ranges. Based on the solution diagram, an efficient fast Riemann solver was also developed. Moreover, small perturbation analysis was performed to demonstrate the relations between the primitive variables, velocity and pressure, for the Riemann problem. The typical shock‐tube problem and the water‐hammer problem were implemented as sample ones to test the numerical method. It was shown that the present numerical method incorporated with Van Leer's flux limiter is a promising one to simulate fluid transient problem for piping in the present study. Copyright © 2002 John Wiley & Sons, Ltd.     

Characters of unipotent radicals of standard parabolic subgroups with 3 parts

Journal of Algebraic Combinatorics - This paper gives explicit constructions of all irreducible representations of unipotent radicals $$N_{n_1,n_2,n_3}({\mathbb {F}}_q)$$ of the standard parabolic...     

Superoxide Stabilization and a Universal KO2 Growth Mechanism in Potassium–Oxygen Batteries

Rechargeable potassium–oxygen (K‐O₂) batteries promise to provide higher round‐trip efficiency and cycle life than other alkali–oxygen batteries with satisfactory gravimetric energy density (935 Wh kg^?1). Exploiting a strong electron‐donating solvent, for example, dimethyl sulfoxide (DMSO) strongly stabilizes the discharge product (KO₂), resulting in significant improvement in electrode kinetics and chemical/electrochemical reversibility. The first DMSO‐based K‐O₂ battery demonstrates a much higher energy efficiency and stability than the glyme‐based electrolyte. A universal KO₂ growth model is developed and it is demonstrated that the ideal solvent for K‐O₂ batteries should strongly stabilize superoxide (strong donor ability) to obtain high electrode kinetics and reversibility while providing fast oxygen diffusion to achieve high discharge capacity. This work elucidates key electrolyte properties that control the efficiency and reversibility of K‐O₂ batteries.