A novel tridentate nitrogen donor as ligand in copper catalyzed ATRP of methyl methacrylate

A tridentate ligand, BPIEP: 2,6‐bis[1‐(2,6‐diisopropyl phenylimino) ethyl] pyridine, having central pyridine unit and two peripheral imine coordination sites was effectively employed in controlled/“living” radical polymerization of MMA at 90°C in toluene as solvent, Cu^IBr as catalyst, and ethyl‐2‐bromoisobutyrate (EBiB) as initiator resulting in well‐defined polymers with polydispersities M_w/M_n ≤ 1.23. The rate of polymerization follows first‐order kinetics, k_app = 3.4 × 10^?5 s^?1, indicating the presence of low radical concentration ([P*] ≤ 10^?8) throughout the reaction. The polymerization rate attains a maximum at a ligand‐to‐metal ratio of 2:1 in toluene at 90°C. The solvent concentration (v/v, with respect to monomer) has a significant effect on the polymerization kinetics. The polymerization is faster in polar solvents like, diphenylether, and anisole, as compared to toluene. Increasing the monomer concentration in toluene resulted in a better control of polymerization. The molecular weights (M_n,SEC) increased linearly with conversion and were found to be higher than predicted molecular (M_n,Cal). However, the polydispersity remained narrow, i.e., ≤1.23. The initiator efficiency at lower monomer concentration approaches a value of 0.7 in 110 min as compared to 0.5 in 330 min at higher monomer concentration. The aging of the copper salt complexed with BPIEP had a beneficial effect and resulted in polymers with narrow polydispersitities and higher conversion. PMMA obtained at room temperature in toluene (33%, v/v) gave PDI of 1.22 (M_n = 8500) in 48 h whereas, at 50°C the PDI is 1.18 (M_n = 10,300), which is achieved in 23 h. The plot of lnk_app versus 1/T gave an apparent activation energy of polymerization as (ΔE^≠_app) 58.29 KJ/mol and enthalpy of equilibrium (ΔH⁰_eq) to 28.8 KJ/mol. Reverse ATRP of MMA was successfully performed using AIBN in bulk as well as solution. The controlled nature of the polymerization reaction was established through kinetic studies and chain extension experiments. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4996–5008, 2005     

Tribute to Endre Csáki and Pál Révész

Summary This article provides a glimpse of some of the highlights of the joint work of Endre Csáki and Pál Révész since 1979. The topics of this short exploration of the rich stochastic milieu of this inspiring collaboration revolve around Brownian motion, random walks and their long excursions, local times and additive functionals, iterated processes, almost sure local and global central limit theorems, integral functionals of geometric stochastic processes, favourite sites--favourite values and jump sizes for random walk and Brownian motion, random walking in a random scenery, and large void zones and occupation times for coalescing random walks.     

一类流行病数学模型解的研究

该文讨论了一类非线性抛物型方程组解的性质，利用微分方程上、下解方法证明了初值适当小时，方程存在整体解；初值适当大时，解在有限时间上爆破，推广了文献[1]的结果．     

"藏汇于国"到"藏汇于民"的外汇投资渠道探讨

为了更好地落实藏汇于民,必须拓展外汇投资渠道,使藏汇于民成为可能。文章主要探讨当前可能的主要外汇投资渠道,并就在外汇投资活动中需要注意的事项给予说明。     

阳高县沼气池建设的实践

从规划、标准、质量、管护、政策扶持和市场运作等方面介绍了阳高县沼气池建设的实践。     

Bounds to optimal burn‐in and optimal work size

Burn‐in is a widely used method to improve the quality of products or systems after they have been produced. In this paper, we consider the problem of determining the optimal burn‐in time and optimal work size maximizing the long‐run average amount of work saved per time unit in the computer applications. Assuming that the underlying lifetime distribution of the computer has an initially decreasing or/and eventually increasing failure rate function, an upper bound for the optimal burn‐in time is derived for each fixed work size and a uniform (with respect to the burn‐in time) upper bound for the optimal work size is also obtained. Furthermore, it is shown that a non‐trivial lower bound for the optimal burn‐in time can be derived if the underlying lifetime distribution has a large initial failure rate. Copyright © 2005 John Wiley & Sons, Ltd.     

对流扩散方程的一种新型差分格式

对流扩散方程可以描述众多的物理化学现象，因而对其寻求稳定的，实用的数值解法有着重要的现实意义。本文针对形式较一般的一维非定常对流扩散方程，构造了对角元严格占优的Crank-Nicholson差分格式，然后对其分别用分离变量的方法以及能量估计的方法作了稳定性的分析，最后给出了数值试验的结果，数值结果表明本文构造的格式能够较好的处理经典的Crank-Nicholson格式所不能处理的对流项系数较大的对流扩散方程，并具有较好的精度。     

Benzene fused five-membered heterocycles. A theoretical approach

The Nuclear Independent Chemical Shift of each ring, as a criterion of aromaticity, is used to explain the stability order of benzopyrrole, benzofuran and benzothiophene, and their isomers. The results indicate that the benzene ring is aromatic in all the systems. The five-membered rings of benzopyrrole, benzofuran and benzothiophene are also aromatic, whereas those of isobenzopyrrole, isobenzofuran and isobenzothiophene are non-aromatic. This could be an explanation of the stability of the former molecules. The molecular orbitals and the condensed Fukui functions derived from the electronic structure calculations are also reported. These reactivity indices explain the expected electrophilic substitution of these compounds. The theoretical structure, ionization energies, order of aromaticity, stability and reactivity are in good agreement with the experimental results. The usefulness of this approach to determine the reactivity is discussed since their stability and reactivity may be understood. The reactivity indices are useful to explain and confirm the experimental information, and for molecules with unknown reactive behavior, this approach could help to predict some of the reactions.     

Fractional Brownian Heavy Traffic Approximations of Multiclass Feedforward Queueing Networks

We consider multiclass feedforward queueing networks under first in first out and priority service disciplines driven by long-range dependent arrival and service time processes. We show that in critical loading the normalized workload, queue length and sojourn time processes can converge to a multi-dimensional reflected fractional Brownian motion. This weak heavy traffic approximation is deduced from a deterministic pathwise approximation of the network behavior close to constant critical load in terms of the solution of a Skorokhod problem. Since we model the doubly infinite time interval, our results directly cover the stationary case.AMS subject classification: primary 90B15, secondary 60K25, 68M20