Mechanism of the reaction of neutral and anionic N-nucleophiles with α-halocarbonyl compounds

N-Acylalkylation of neutral and anionic N-nucleophiles with α-halocarbonyl compounds was investigated by quantum chemical methods in terms of the density functional theory and by experimental methods for 2,3-dihydroimidazo[2,1-b]quinazolin-1(10)H-5-one, its N-anion, and simpler model structures. High reactivity of these reagents is determined primarily by stabilization of transition states (TS) by bridge bonds involving halogen or nitrogen atoms rather than by conjugation, as has been commonly accepted. Bridged TS are formed by both the substitution mechanism S _N 2 and the addition-elimination mechanism. α-Haloalkyl-substituted zwitterions, which are potential intermediates of stepwise N-acylalkylation of neutral N-nucleophiles, do not exist in the isolated state, but they are rather efficiently stabilized upon solvation. These zwitterions, as well as analogous O-anions generated from anionic N-nucleophiles, can serve as intermediates of N-acylalkylation, as was demonstrated by localization of the corresponding TS. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1150–1164, June, 2007.     

物理实验课程考核、评估体系初探

对物理实验课程考核、评估方法进行了探讨，提出了物理实验课程考核、评估体系及实施细则．重点介绍了体系中的核心部分——正规的物理实验课程考试．     

A comparative study on the interaction between tin(II) porphyrin and selected group 8B metals for potential application as reduction catalysts

We study the interaction between tin(II) porphyrin (SnPor) with platinum and non-precious Group 8B metals (iron, cobalt and nickel) by density functional theory and discuss the electronic properties of the resulting products. We also model the interaction of the resulting compounds with water where applicable. Our studies indicate that, SnPor-Ni possesses electronic properties similar to SnPor-Pt, suggesting that it may possess similar photocatalytic properties for reduction reactions, such as converting water to hydrogen gas.     

基于离差最大化原理的灰色综合评判方法及其应用

在灰色综合隶属度评价方法基础上,按照离差最大化原理,提出了一种品种区域试验的新的确定权重的方法.应用这种方法,对2002-2003年度国家黄淮南片小麦冬水组区域试验进行了分析.结果表明,这种分析方法克服了通常专家调查法和层次分析法主观随意性强的缺点,因而其分析结果更加客观、可靠.大面积生产实践也表明该方法具有一定可行性和有效性.     

Weighted Kolmogrov–Smirnov type tests for grouped Rayleigh data

We consider goodness of fit tests for the Rayleigh distribution with grouped data. New Kolmogrov–Smirnov type tests are suggested and compared with the traditional chi-square and likelihood ratio tests. The results show that some of the suggested tests have a good power performance as compared with the traditional ones.     

Tests for Varying G

In this note we consider a variable G cosmology which is consistent with observation and which had successfully predicted an ever expanding accelerating universe with a small cosmological constant amongst other things. Three further tests are proposed in this note: First, the inexplicable anomalous accelerations of the Pioneer spacecrafts can be explained. It is then shown that the observed shortening of the orbital periods of binary pulsars is in good agreement with this model. Finally, more general changes in orbital parameters are deduced, which may be observed in the future.     

Scientific legacy of Stanley Ruby

Stanley L. Ruby (1924–2004) made major contributions to Mössbauer spectroscopy and was the first to suggest the feasibility of observing the Mössbauer effect using synchrotron radiation. In this article we recall his scientific legacy that have inspired his scientific colleagues.     

Imidazol(in)ium carboxylates as N-heterocyclic carbene ligand precursors for Suzuki-Miyaura reactions

Simple catalysts formed in situ from palladium acetate and a variety of imidazolium and imidazolinium carboxylates and dithiocarboxylates have been screened in the coupling of aryl halides with trans-2-phenylvinylboronic acid. Imidazol(in)ium carboxylates show an excellent activity, which compares to that displayed by the parent imidazol(in)ium chlorides, whereas imidazol(in)ium dithiocarboxylates are poorly efficient. Interestingly, the base employed exerts a profound influence on the trans/cis stereochemistry of the coupling product.     

火工品可靠性试验数据的综合分析方法

升降法试验数据和固定刺激量下的成败型试验数据,是两种最常见的火工品可靠性试验数据．我们应用Markov链,研究了升降法试验数据下,感度分布参数的极大似然估计的特性．在此基础上,应用Bootstrap方法和Bayes方法,给出了综合分析两种试验数据的方法．最后,将该方法应用于520底火的可靠性鉴定,得出了有益的结论．     

Optical spectroscopy of Yb/Er codoped NaY(WO4)2 crystal

Erbium and ytterbium codoped double tungstates NaY(WO₄)₂ crystals were prepared by using Czochralski (CZ) pulling method. The absorption spectra in the region 290-2000 nm have been recorded at room temperature. The Judd-Ofelt theory was applied to the measured values of absorption line strengths to evaluate the spontaneous emission probabilities and stimulated emission cross sections of Er³⁺ ions in NaY(WO₄)₂ crystals. Intensive green and red lights were measured when the sample were pumped by a 974 nm laser diode (LD), especially, the intensities of green upconversion luminescence are very strong. The mechanism of energy transfer from Yb³⁺ to Er³⁺ ions was analyzed. Energy transfer and nonradiative relaxation played an important role in the upconversion process. Photoexcited luminescence experiments are also fulfilled to help analyzing the transit processes of the energy levels.