The NMR spectra of porphyrins—14: Self-aggregation of zinc(II) meso-nitro and meso-dinitro octaethylporphyrins

Complex formation in zinc(II) meso-nitro-octa-ethylporphyrin (1) and the corresponding α,β-dinitro (2) and α, γ-dinitro (3) zinc(II) chelates has been studied using proton NMR at 220MHz. This allows complete resolution of all the distinct groups in the proton spectrum, and the large concentration dependence of the spectra of 1 and 2 can be analysed to afford the monomeric and monomer-dimer shifts for all protons in these molecules. In contrast 3 shows no concentration dependence, nor any change upon addition of pyrrolidine, which immediately dissociates the aggregates of 1 and 2. The monomeric ¹H and ¹³C shifts are reported, together with those of zinc(II) octaethylporphyrin (4), and the complete assignment given allows the substituent shifts of the meso nitro groups in the porphyrin to be obtained. Analysis of the monomer-dimer shifts in terms of the ring current model gives the detailed geometries of the dimers, which have an inter-ring separation of ca 4.5 Å and a lateral displacement from the vertical of ca 1.0 Å. The results also allow the distinction between two different molecular complexes considered previously, and fully confirm our earlier suggestions that binding is due to metal-to-porphyrin, rather than metal-to-substituent, interactions.     

灰竹挥发油化学成分分析

用溶剂提取法提取了灰竹的挥发性物质,用GC－MS法鉴定出22种化合物,其中主要成分（相对含量）为烯类（19．0％）,醇类（39．9％）,酯类（1．0％）、酸类（10．9％）,酮类（2．3％）、芳香烃类（19．8％）和烷烃类（3．6％）化合物,占总检出量约97％。     

桔梗等中药微量元素初探

对中药桔梗、怀牛膝,华山参、鹿角胶,龟甲胶及阿胶进行了微量元素研究。结果发现：同一种中药因产地不同,其微量元素的含量不同。同一种植物药,其部位不同,所含微量元素多少不等。同一类型的中药,其品种、来源不同,微量元素的含量高低也不相同。本研究为今后对这些中药进行真伪鉴别,合理开发或综合利用都提供了科学的依据。     

Identification of the convective instability in a multi-component solution by 3D simulations

Three-dimensional calculations have been done to simulate the onset of convective motion in ternary nondilute solution under phase transition conditions. The process is considered for Rayleigh number in the range $[1\times {10}^3,1.4\times {10}^4]$, where subcritical convective motion with hexagonal flow pattern is identified. The results are in good agreement with the linear and finite amplitude theory of hydrodynamics instability. To cite this article: V.V. Kolmychkov et al., C. R. Mecanique 333 (2005).     

Uncapacitated Euclidean Hub Location: Strengthened Formulation,New Facets and a Relax-and-cut Algorithm

The multiple allocation uncapacitated hub location problem is considered. This problem arises in transportation systems when several locations send and receive passengers and/or express packages and the performance of these systems can be improved by using transshipment points (hubs), where the passengers/packages are collected and distributed. An Integer Programming formulation, the one giving the best computational results until now, serves as a basis for the solution method. Using the fact that the transportation costs between hubs satisfy the triangle inequality, an analysis of the set of solutions that are not candidates to be optimal is carried out and, as a consequence, the formulation of the problem can be strengthened by means of powerful valid inequalities obtained through the study of the intersection graph of an associated set packing problem. The algorithm developed uses the most promising of these inequalities in a Lagrangian relaxation context to reduce the size of the branching tree and improve the computational times. This improvement is shown by means of a computational study, where a set of instances are optimally solved with low computational effort.     

Groupe Des Inversibles Et Rayon Spectral Dans Les Algèbres Topologiques

We deal with the relationship between the spectral radius and the topological bihaviour of the group of invertible elements in a topological algebra, introducing accordingly several types of (generalized Q-) algebras. We then give properties and characterizations of such algebras. Applications to weighted algebras as well as several classes of examples are provided.

     

Zinc-porphyrin sensitized reduction of simple and functional quinones in vesicle systems

Changes of the surfactant vesicle sizes and of the efficiency of the photoredox reaction between various solubilized Zn porphyrins and duroquinones upon incorporation of the chromophore or upon addition of salts have been examined by quasi-elastic light scattering and laser photolysis techniques. The yields of porphyrin cation and duroqumone anion radicals appear to be independent of the nature of the porphyrin-qumone system. Addition of salts influences both the yield and the ejection of porphyrin cations from the vesicles by screening up the surface charge.     

Détermination de la réponse asymptotique d'une structure anélastique sous chargement thermomécanique cycliqueDetermination of the asymptotic response of a structure under cyclic thermomechanical loading

A method for the solution of cyclic thermomechanical nonlinear problems is presented: it is a Direct Cyclic Method which is an alternative approach to classical methods. It consists in directly seeking the asymptotic response of an inelastic structure subjected to a periodic thermomechanical loading without following the loading path. It is based on the Large Time Increment Method, the periodicity of the limit state and the Fourier transform. To cite this article: M.H. Maitournam et al., C. R. Mecanique 330 (2002) 703–708.     

The electrochemical determination of oxygen ion diffusion coefficients in La0.50Sr0.50CoO3−y: Experimental results and related properties

Results of an electrochemical method for the determination of oxygen ion diffusion coefficients D_O^2? in porous pellets of La_0.50Sr_0.50CoO_3?y are presented. Log D_O^2? can be expressed as log D_O^2?=?(2.3±0.2) 10³/T?(6.6±0.6) cm² s^?1. The activation energy E_a for the diffusion process equals 44 kJ mol^?1. Further the related electrochemical measurement and the adjustment of the oxygen deficiency y are described. At 75°C the following empirical Nernst relation between the electrode potential E (vs. a Pt/H₂ (1 atm) electrode in the same solution) and Δy is found: E=627–108 ln (Δy + 0.0054) mV. (Δy=y?y₀; y₀=mole fraction of vacancies at the reversible O₂ potential of 1190 mV). The use of La_0.50Sr_0.50CoO_3?y as a solid solution electrode in practical storage cells seems to be excluded for thermodynamic and kinetic reasons.