Thermal behaviour of the homopolynuclear glyoxylate complex combinations with Cu(II) and Cr(III)

Homopolynuclear complexes of Cu(II) respectively Cr(III) with the glyoxylate dianion, C₂H₂O₄ ^2-, have been studied in non-isothermal regime in air and nitrogen. The results of the non-isothermal analysis performed for the synthesised complexes, Cu(C₂H₂O₄)·0.5H₂O, respectively [Cr₂(OH)₂(C₂H₂O₄)₂(OH₂)₄]·2H₂O, correlated with the results of the IR and TG analysis of the compounds obtained by thermal treatment from the initial complexes and the results of the GLC and XR analysis have led to the establishment of the thermal decomposition mechanisms for the two studied complexes. The decomposition mechanisms confirm the stoichiometric and structural formulae proposed for the two synthesised homopolynuclear complexes. This revised version was published online in July 2006 with corrections to the Cover Date.     

氢化物石墨炉原子吸收光谱法应用研究——Ⅱ.超痕量汞的测定

本文使用涂金石墨管,自制氢化物石墨炉进样系统及连续流动氢化物发生器,直接测定了粮食,植物及水中的痕量汞。该法实用性强,线性范围宽,精密度好,准确度高。灵敏度为1.1ng/L,检出限(3σ)为0.8ng/L。     

Zirconium bis(indenyl) sandwich complexes with an unprecedented indenyl coordination mode and their role in the reactivity of the parent bent-metallocenes: a detailed DFT mechanistic study

The mechanisms of three closely related reactions were studied in detail by means of DFT/B3 LYP calculations with a VDZP basis set. Those reactions correspond to 1) the reductive elimination of methane from [Zr(eta5-Ind)2(CH3)(H)] (Ind=C9H7-, indenyl), 2) the formation of the THF adduct, [Zr(eta5-Ind)(eta6-Ind)(thf)] and 3) the interconversion between the two indenyl ligands in the Zr sandwich complex, [Zr(eta5-Ind)(eta9-Ind)], which forms the link between the two former reactions. An analysis of the electronic structure of this species indicates a saturated 18-electron complex. A full understanding of the indenyl interchange process required the characterisation of several isomers of the Zr-bis(indenyl) species, corresponding to different spin states (S=0 and S=1), different coordination modes of the two indenyl ligands (eta5/eta9, eta5/eta5 and eta6/eta9), and three conformations for each isomer (syn, anti, and gauche). The fluxionality observed was found to occur in a mechanism involving bis(eta5-Ind) intermediates, and the calculated activation energy (11-14 kcal mol(-1)) compares very well with the experimental values. Two alternative mechanisms were explored for the reductive elimination of methane from the methyl/hydride complex. In the more favourable one, the initial complex, [Zr(eta5-Ind)2(CH3)(H)], yields [Zr(eta5-Ind)2] and methane in one crucial step, followed by a smooth transition of the Zr intermediate to the more stable eta5/eta9-species. The overall activation energy calculated (Ea=29 kcal mol(-1)) compares well with experimental values for related species. The formation of the THF adduct follows a one step mechanism from the appropriate conformer of the [Zr(eta5-Ind)(eta9-Ind)] complex, producing easily (Ea=6.5 kcal mol(-1)) the known product, [Zr(eta5-Ind)(eta6-Ind)(thf)], a species previously characterised by X-ray crystallography. This complex was found to be trapped in a potential well that prevents it from evolving to the 3.4 kcal mol(-1) more stable isomer, [Zr(eta5-Ind)2(thf)], with both indenyl ligands in a eta5-coordination mode and a spin-triplet state (S=1).     

考虑大数据营销和风险规避的绿色供应链决策与协调

通过建立考虑大数据营销及零售商风险规避的博弈模型,对绿色供应链定价、产品绿色度及利润进行比较分析。研究发现:无论集中决策、双方风险中性分散决策还是仅零售商风险规避分散决策,考虑大数据营销时的供应链整体期望利润和产品绿色度较高,且大数据营销效率因子对产品绿色度的增加有正向作用;双方风险中性分散决策下,一定条件下,两部定价契约能够有效协调供应链整体利润,实现帕累托改进;仅零售商风险规避分散决策下,零售商的风险规避行为会降低其对大数据营销的投入,一定条件下,两部定价契约也能够实现供应链整体期望利润的帕累托改进。     

A genetic algorithm for the automated generation of molecules within constraints

Summary A genetic algorithm has been designed which generates molecular structures within constraints. The constraints may be any useful function, for example an enzyme active site, a pharmacophore or molecular properties from pattern recognition or rule-induction analyses. The starting point may be random or may utilise known molecules. These are modified to grow into families of structures which, using the evolutionary operators of selection, crossover and mutation evolve to better fit the constraints. The basis of the algorithm is described together with some applications in lead generation, 3D database construction and drug design. Genetic algorithms of this type may have wider applications in chemistry, for example in the design and optimisation of new polymers, materials (e.g. superconducting materials) or synthetic enzymes.     

Characterization of tension and normally lignified wood cellulose inPopulus maximowiczii

We have investigated unlignified tension wood and normally lignified wood celluloses inPopulus maximowiczii with particular reference to the composition of two crystalline phases I/I (triclinic/ monoclinic). Four independent techniques, which enable us to detect the two phases, CP/MAS¹³C NMR, Fourier transform infrared microscopy, selected-area electron diffraction, and X-ray diffraction were applied. Because of the low crystallinity of wood celluloses, particularly in the case of celluloses in the lignified cell wall, no single method was decisive enough to be able to determine the composition of the two phases as one can with highly crystalline materials. The I dominant structure (monoclinic crystal type) was, however, preferred for both tension and normal wood celluloses.     

Optimizing constrained subtrees of trees

Given a treeG = (V, E) and a weight function defined on subsets of its nodes, we consider two associated problems. The first, called the rooted subtree problem, is to find a maximum weight subtree, with a specified root, from a given set of subtrees.The second problem, called the subtree packing problem, is to find a maximum weight packing of node disjoint subtrees chosen from a given set of subtrees, where the value of each subtree may depend on its root.We show that the complexity status of both problems is related, and that the subtree packing problem is polynomial if and only if each rooted subtree problem is polynomial. In addition we show that the convex hulls of the feasible solutions to both problems are related: the convex hull of solutions to the packing problem is given by pasting together the convex hulls of the rooted subtree problems.We examine in detail the case where the set of feasible subtrees rooted at nodei consists of all subtrees with at mostk nodes. For this case we derive valid inequalities, and specify the convex hull whenk 4.Research supported in part by Nato Collaborative Research Grant CRG 900281, Science Program SC1-CT91-620 of the EEC, and contract No 26 of the programme Pôle d'attraction interuniversitaire of the Belgian government.     

Randomized algorithms for the separation of point sets and for solving quadratic programs

A randomized algorithm for finding a hyperplane separating two finite point sets in the Euclidean space ^d and a randomized algorithm for solving linearly constrained general convex quadratic problems are proposed. The expected running time of the separating algorithm isO(dd! (m + n)), wherem andn are cardinalities of sets to be separated. The expected running time of the algorithm for solving quadratic problems isO(dd! s) wheres is the number of inequality constraints. These algorithms are based on the ideas of Seidel's linear programming algorithm [6]. They are closely related to algorithms of [8], [2], and [9] and belong to an abstract class of algorithms investigated in [1]. The algorithm for solving quadratic problems has some features of the one proposed in [7].This research was done when the author was supported by the Alexander von Humboldt Foundation, Germany.On leave from the Institute of Mathematics and Mechanics, Ural Department of the Russian Academy of Sciences, 620219 Ekaterinburg, S. Kovalevskaya str. 16, Russia.     

The host-guest chemistry of resorcinarenes

Conformations, acid-base and supramolecular properties of phenolic metacyclophanes obtained from the condensation of resorcinol with aldehydes are discussed, including the mechanisms involved in the formation of these macrocycles. The strong binding of choline-type compounds and the inhibition of acetylcholine hydrolysis with therccc stereoisomers is mechanistically evaluated; arctt isomer shows strong conformational coupling for, e.g., choline binding and simultaneous proton release. The presence of larger alkyl residues at the bottom of therccc macrocycle leads to an additional binding site for small lipophilic substrates, which is independent of the upper complexation center for positively charged substrates. Substitution at the upper rim by carboxylic groups at the 2-position of the phenyl rings yields receptors for, e.g., , -diammonium ions with alternate equatorial and axial arylunits. Positively charged substituents at the upper rim, introduced by aminoalkylation, lead to little change of complexation as a result from their orientation away from the binding center. Aminoacid substituents, for the same reason, do not lead to enantioselective complexation, but allow particularly for strong binding of transition metal ions. Preliminary studies show that resorcinarenes bearing a wide array of positive charges are potent groove binders to ds-DNA without intercalative contributions.This paper is dedicated to the commemorative issue on the 50th anniversary of calixarenes.     

Investigation of superconductivity effects in single-phase and multiphase Bi2Sr2CaCu2O8 single-crystals at 2-MM wavelengths

Experimental investigations of superconductivity effects in single-phase and multiphase Bi₂Sr₂CaCu₂O₈ single-crystals have been carried out at 142 GHz frequency by means of the standing wave profile method [1]. Josephson harmonic generation has been observed to be responsible for the appearence of additional peaks on the standing wave profile of the open dielectric resonator loaded with a properly orientated multiphase high-T_c superconductor specimen. This leads to the conclusion that most of the Josephson junctions in multiphase crystals are located in certain crystallographic planes. The investigations of temperature dependencies showed that sharp resonant peaks of conductivity observed earlier [2] at 60 GHz could also be observed at 142 GHz.