Synthesis of alkyl α- and β-<Emphasis Type="SmallCaps">d</Emphasis>-glucopyranoside-based chiral crown ethers and their application as enantioselective phase-transfer catalysts

Chiral monoaza-15-crown-5-type lariat ethers annelated to alkyl 4,6-O-benzylidene-α- and β-d-glucopyranosides have been synthesized. These macrocycles generated significant asymmetric induction as phase-transfer catalysts in a few two-phase reactions. The catalytic effect of the lariat ethers with methoxy, ethoxy, and i-propoxy substituents on C-1 of the sugar unit in both α and β positions was compared. In liquid–liquid two-phase reactions, the nature and position of the substituents did not have much effect. The α-anomers were somewhat more efficient in terms of enantioselectivity than the β forms. In asymmetric Darzens condensations, in the epoxidation of trans-chalcone, in the Michael addition of β-nitrostyrene and diethyl acetamidomalonate, and in the reaction of 2-benzylidene-1,3-indandione with diethyl bromomalonate, maximum enantioselectivities of 73, 94, 78, and 72%, respectively, were obtained in presence of glucopyranoside-based lariat ethers as catalysts.     

Online and Quasi-online Colorings of Wedges and Intervals

We consider proper online colorings of hypergraphs defined by geometric regions. We prove that there is an online coloring algorithm that colors N intervals of the real line using \({\Theta }(\log N/k)\) colors such that for every point p, contained in at least k intervals, not all the intervals containing p have the same color. We also prove the corresponding result about online coloring a family of wedges (quadrants) in the plane that are the translates of a given fixed wedge. These results contrast the results of the first and third author showing that in the quasi-online setting 12 colors are enough to color wedges (independent of N and k). We also consider quasi-online coloring of intervals. In all cases we present efficient coloring algorithms.     

小型射流发生器的实验研究

 通过对小型射流单重态氧发生器的稳定工作条件及射流板性能对发生器的性能影响的考察,在一个小型超音速氧碘化学激光器（COIL）中使用射流发生器成功地得到激光输出。     

一维大气边界层光学折射率结构常数数值模式的实验检验

提出了一种大气光学折射率结构常数的数值模式。一次输入日期、时间、经纬度、温度、湿度、风速、粗糙度、土壤参数，云量等相关参数，可得到24h内的温度、湿度、风场、折射率结构常数等量。通过与实测对比表明，无论是月平均折射率结构常数还是某天的折射率结构常数，模式计算与实测数据都符合得很好。模式计算的向下总辐射通量与实测数据基本一致。     

团簇Ni4P催化析氢性能研究

为探究团簇Ni₄P催化析氢最强的结构,基于密度泛函理论,在B3LYP/Lan12dz水平下,对团簇Ni₄P的初始构型进行计算和优化,得到5种优化构型。从热力学稳定性、前线轨道图和前线轨道能级差对团簇Ni₄P的析氢性能分析发现,构型1^（4）和1^（2）的热力学稳定性较强;团簇Ni₄P各优化构型均易吸附水中的氢原子,Ni原子为团簇Ni₄P催化活性位点,且构型1^（4）、1^（2）和2^（4）催化析氢的活性更强。(1^（2）)-H、(2^（2）)-H在电化学脱附法和化学重组法中均具有较强的催化活性。以上说明构型1^（2）是团簇Ni₄P催化析氢最强的结构。     

Linearity of the core correspondence

Bloch and de Clippel (J Econ Theory 145:2424–2434, 2010) characterized sets of balanced TU-games on which the core correspondence is linear by means of an equivalence relation. We characterize maximal regions on which the core correspondence is linear in four different ways. First, by finitely many linear equalities and inequalities; thus, the core is piecewise linear. Second, maximal linear regions coincide with closures of equivalence classes (in the sense of Bloch and de Clippel) that are maximal w.r.t. set inclusion. Third, maximal linear regions coincide with closures of equivalence classes of full dimension. Fourth, for every extreme point of the core of a game in the interior of a maximal linear region, the collection of tight core inequalities constitutes a basis.     

Synthesis and biological activity of alkylidene-substituted cephems and penams

The condensation of tert-butyl esters of 3-methyl-7-oxoceph-3-em-4-carboxylic and 6-oxopenicillanic acids with a series of 2-oxoalkylidene(triphenyl)phosphoranes gave tert-butyl esters of new cephalosporin and penicillin analogs with an alkylidene substituent in the β-lactam ring. Most of these products were oxidized by meta-chloroperbenzoic acid to the corresponding sulfones. The cephemes and penams synthesized including the oxidized products displayed high cytotoxicity relative to cancer cells in vitro. Some of the alkylidene-substituted cephems as the free acids, similar to Tazobactam, inhibit the catalytic activity of Enterobacter cloacae penicillinase.     

Oximes of five-membered heterocyclic compounds with three and four heteroatoms 2. Synthesis of derivatives,reactions, and biological activity (Review)

Data on the reactions of triazole, tetrazole, dioxazole, oxadiazole, and thiadiazole aldoximes, ketoximes, and amidoximes, their synthesis, and the reactions of their derivatives are reviewed. The synthesis of new heterocycles based on the oximes of five-membered heterocyclic compounds with three and four heteroatoms is examined separately. The principal results from investigation of the biological activity of ethers of these oximes are also presented. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 963–990, July, 2008.     

钳形酰腙类阴离子受体的合成及识别性质研究

设计合成了基于吲哚酰腙单元的钳形阴离子受体(1),UV-Vis滴定实验表明,它在含1%DMSO的CH3CN溶液中能选择性识别具有重要生物学意义的F-、Ac O-和H2PO4-(结合比均为1∶1且Ka104L/mol),但对Cl-、Br-、I-、NO3-、N3-、HSO4-和Cl O4-无识别作用。与它相比,端基为苯并呋喃的参照化合物2在同样溶剂中对上述3种阴离子的亲和性减弱,尤其是对H2PO4-。核磁滴定实验表明,受体1中的吲哚环NH和酰胺NH能产生协同效应,从而对阴离子产生了强效键合作用。