Macrocyclization of polymers via ring‐closing metathesis and azide/alkyne‐“click”‐reactions: An approach to cyclic polyisobutylenes

The end‐to‐end cyclization of telechelic polyisobutylenes (PIB's) toward cyclic polyisobutylenes is reported, using either ring‐closing metathesis (RCM) or the azide/alkyne‐“click”‐reaction. The first approach uses bisallyl‐telchelic PIB's (M_n = 1650, 3680, 9770 g mol^?1) and Grubbs 1st‐, 2nd‐, and 3rd‐generation catalyst leading to cyclic PIB's in 60–80% yield, with narrow polydispersities (M_w/M_n = 1.25). Azide/alkyne‐“click”‐reactions of bisalkyne‐telechelic PIB's (M_n = 3840 and 9820 g mol^?1) with excess of 1,11‐diazido‐undecane leads to the formation of mixtures of linear/cyclic PIB's under formation of oligomeric cycles. Subsequent reaction of the residual azide‐moieties in the linear PIB's with excess of alkyne‐telechelic PEO enables the chromatographic removal of the resulting linear PEO‐PIB‐block copolymers by column chromatography. Thus pure cyclic PIB's can be obtained using this double‐“click”‐method, devoid of linear contaminants. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 671–680, 2010     

Enhancement of Mn red emission in CaGa2S4 compounds by co-doping rare-earth elements

When certain trivalent rare-earth ions (Ln's) are co-doped in CaGa₂S₄:Mn²⁺ as sensitizers, the Mn red emission of the compound is strikingly enhanced. In this work, efficiency of each lanthanide is studied. The best efficiencies are achieved with La³⁺-, Pr³⁺-, and Tb³⁺- co-doped compounds, for each of which the effects of concentrations of the co-doped ions on the Mn²⁺ emission are investigated. The energy-transfer mechanisms and the location of electronic energy levels of both the trivalent and the divalent lanthanides in the energy band gap of the host material are discussed. Depending on Ln's, charge transfer or cross-relaxation should be taken into account.     

Fluorescence quenching of 9-cyanoanthracene in presence of zinc tetraphenylporphyrin in a polar liquid medium

Steady-state and time-resolved techniques are used to study photoinduced electron and/or excitational energy transfer processes involved within a novel donor (zinc tetraphenylporphyrin)-acceptor (9-cyanoanthracene) system in a polar liquid medium (acetonitrile) at the ambient temperature (300 K). After photoexcitation of 9-cyanoanthracene, its fluorescence emission as well as lifetime are found to be quenched in presence of zinc tetraphenylporphyrin. The fluorescence quenching is ascribed to be due to the combined effect of electron transfer from zinc tetraphenylporphyrin to 9-cyanoanthracene and energy transfer (radiative as well as non-radiative) from 9-cyanoanthracene to zinc tetraphenylporphyrin. The highly exergonic values of Gibbs free energy change for both forward electron transfer reaction (−1.15 eV) and charge recombination reaction (−1.94 eV) indicate the possibilities of occurrences of these two processes in the Marcus inverted region. The fluorescence quenching rate due to photoinduced electron transfer reaction is found to be close to the diffusion-controlled limit within the present donor-acceptor system upon excitation of the acceptor molecules.     

Longitudinal and bulk viscosities of binary fluid mixtures

Expressions for zeroth, second and fourth sum rules of longitudinal and bulk stress auto correlation functions have been derived for binary fluid mixtures. Longitudinal and bulk viscosities of an Ar–Kr mixture have been calculated using Mori's memory function formalism coupled with the sum rules of longitudinal and bulk stress auto correlation functions. The results obtained are compared with the molecular dynamics simulation. Mass dependence of the longitudinal and bulk viscosities has been studied for different compositions of an isotopic mixture at different densities and temperatures. For very large mass ratio, the longitudinal and bulk viscosities of the isotopic mixture are more dependent on mole fraction than on mass.     

Non-Uniformity and Generalised Sacks Splitting

We show that there do not exist computable functions f ₁(e, i), f ₂(e, i), g ₁(e, i), g ₂(e, i) such that for all e, i ∈ ω, (1) $ {\left( {W_{{f_{1} {\left( {e,i} \right)}}} - W_{{f_{2} {\left( {e,i} \right)}}} } \right)} \leqslant _{{\rm T}} {\left( {W_{e} - W_{i} } \right)}; $ (2) $ {\left( {W_{{g_{1} {\left( {e,i} \right)}}} - W_{{g_{2} {\left( {e,i} \right)}}} } \right)} \leqslant _{{\rm T}} {\left( {W_{e} - W_{i} } \right)}; $ (3) $ {\left( {W_{e} - W_{i} } \right)} \not\leqslant _{{\rm T}} {\left( {W_{{f_{1} {\left( {e,i} \right)}}} - W_{{f_{2} {\left( {e,i} \right)}}} } \right)} \oplus {\left( {W_{{g_{1} {\left( {e,i} \right)}}} - W_{{g_{2} {\left( {e,i} \right)}}} } \right)}; $ (4) $ {\left( {W_{e} - W_{i} } \right)} \not\leqslant _{{\rm T}} {\left( {W_{{f_{1} {\left( {e,i} \right)}}} - W_{{f_{2} {\left( {e,i} \right)}}} } \right)}{\text{unless}}{\left( {W_{e} - W_{i} } \right)} \leqslant _{{\rm T}} {\emptyset};{\text{and}} $ (5) $ {\left( {W_{e} - W_{i} } \right)} \leqslant _{{\rm T}} {\left( {W_{{g_{1} {\left( {e,i} \right)}}} - W_{{g_{2} {\left( {e,i} \right)}}} } \right)}{\text{unless}}{\left( {W_{e} - W_{i} } \right)} \leqslant _{{\rm T}} {\emptyset}. $ It follows that the splitting theorems of Sacks and Cooper cannot be combined uniformly.     

Transient Nutation EPR Spectroscopy of Condensed Media (Review)

The application of transient nutations in EPR spectroscopy of condensed media is considered. The main methods of formation and observation of transient nutations are presented. The laws governing this phenomenon in twolevel and multilevel spin systems and also in inhomogeneous broadening of EPR lines are described. Recent advances in the use of transient nutations to separate overlapping spectra, identify quantum numbers and quantum transitions, investigate the kinetics of photoinduced paramagnetic centers, and determine relaxation times for a wide range of crystalline and disordered media are presented.     

无线城域网中中心调度的竞争解决方案

针对无线城域网PMP模式下的竞争问题，提出了一种中心调度的竞争解决方案CSCR（centralized scheduling contention resolution）。通过对每一时间帧内活动用户站（subscriber stations）数目的预测，基站（basestation）给所有用户站提供了一个优化的竞争窗口，所有用户站都采用该窗口独立地参与竞争。理论分析和模拟结果表明，与IEEE802．16推荐的基于二进制指数回退BEB（binary exponential backoff）算法的方案相比，CSCR方案不但易于实现，而且能更加有效地利用无线资源，同时减少请求接入延时。     

On a Theorem of Dubins and Freedman

Under a notion of splitting the existence of a unique invariant probability, and a geometric rate of convergence to it in an appropriate metric, are established for Markov processes on a general state space S generated by iterations of i.i.d. maps on S. As corollaries we derive extensions of earlier results of Dubins and Freedman;⁽¹⁷⁾ Yahav;⁽³⁰⁾ and Bhattacharya and Lee⁽⁶⁾ for monotone maps. The general theorem applies in other contexts as well. It is also shown that the Dubins–Freedman result on the necessity of splitting in the case of increasing maps does not hold for decreasing maps, although the sufficiency part holds for both. In addition, the asymptotic stationarity of the process generated by i.i.d. nondecreasing maps is established without the requirement of continuity. Finally, the theory is applied to the random iteration of two (nonmonotone) quadratic maps each with two repelling fixed points and an attractive period-two orbit.     

UCFC晶体场理论方法（I）——UCFC方法基本概念与d^4组态空间标准基

作为以ｄ４／ｄ６离子为例系统地介绍“ＵＣＦＣ（统一晶场偶合）图象晶体场理论方法”（简称ＵＣＦＣ方法）的系列论文的第一篇，首先介绍了ＵＣＦＣ方法的基本概念，然后介绍了ｄ４／ｄ６离子ＵＣＦＣ方法基本内容的第一部分：ｄ４离子全组态空间标准基链的构造方法。第二篇将介绍如何在标准基链中建造能量矩阵链。第三篇将介绍ｄ４／ｄ６离子ＵＣＦＣ方法的ＥＰＲ理论部分。ＵＣＦＣ方法不仅是一种考虑ｄ电子组态全部多重态的完全计算方法，而且是一种统一的、规范化的、简洁的理论方法体系。它克服了强场、弱场等传统逐次对角化方法的局限性，不须区分晶体场的强弱，因而原则上可通用于任意过渡金属络合物。     

Motion coding of image primitives

We introduce an algorithm for matching stationary or moving image primitive lines between adjacent frames of a video sequence. Starting from local measures of proximity and similarity of shape, the algorithm computes the distance between pairs of primitives. It has strategies for dealing with broken lines and various kinds of connections between lines. The output of the algorithm is used to control a motion coding system, where only unmatched threads need be transmitted. The system can function in a simple conditional replenishment mode, or with motion compensation. Experimental results are reported showing an improvement of compression rate of 2:1 between intraframe primitivebased coding and motion-compensated primitive-based coding.