Chemical Reactivity of Tetrasulfur Tetranitride: Synthesis,Physical Properties,and Structural Characterization of the Amorphous Phase Cu7S4N4

Tetrasulfur tetranitride, S₄N₄, reacts with elemental Cu within inert solvents to a black‐blue material of approximate composition Cu₇S₄N₄ which is totally amorphous to X‐rays and which cannot be made crystalline by either thermal treatment or electron radiation. Cu₇S₄N₄ explodes if heated above 234 °C or when subjected to mechanical shock to eventually yield copper(I) sulfide; this together with the characteristic infrared spectrum of Cu₇S₄N₄ indicates the presence of molecular S₄N₄ units inside the amorphous phase. The metastable nature of Cu₇S₄N₄ is also mirrored by electron microscopy which furthermore allows the structural characterization of its degradation products. Based on experimental EXAFS data offering characteristic Cu—N and Cu—S distances, a theoretical crystalline approximant of Cu₇S₄N₄ was suggested and structurally optimized by density‐functional total‐energy calculations including periodic boundary conditions. This model incorporates a central S₄N₄ unit bonded to three shells of Cu atoms of different functionalities; in addition, a partial rupture of the S₄N₄ unit is likely to allow for a lowering of the total energy of the metastable phase. The latter observation supports the impossibility to make Cu₇S₄N₄ crystallize using ₄N₄ crystallize using whatever kind of measures.     

Taveuniamides: new chlorinated toxins from a mixed assemblage of marine cyanobacteria

Brine shrimp toxicity guided fractionation of the extracts from two mixed Fijian collections of the cyanobacteria Lyngbya majuscula and Schizothrix sp. led to the isolation of eleven novel chlorinated lipids. All of these metabolites show an intriguing constellation of unsaturation (olefinic and acetylenic bonds) and chlorination at the two termini of a 15-carbon chain. The central carbon atom of the chain (C-8) is substituted in each case with an N-acetate function. Taveuniamides A-E have an adjacent carbomethoxy group at C-9 to form a protected β-amino acid while taveuniamides F-K have a methylene group at this position. A standard assortment of 2D NMR techniques in concert with mass spectrometry and other analytical techniques were used to define the structures of these novel metabolites. Taveuniamides F, G and K were the most potent brine shrimp toxins with LD₅₀s between 1.7-1.9 μg/mL.     

N. Charton,A. Feldermann,A. Theis,M. H. Stenzel,T. P. Davis,C. Barner‐Kowollik,Initiator efficiency of 2,2′‐azobis(isobutyronitrile) in bulk dodecyl acrylate free‐radical polymerizations over a wide conversion and molecular weight range (2004) 42(20) 5170–5179

The original article to which this Erratum refers was published in J Polym Sci Part A: Polym Chem (2004) 42(20) 5170–5179. No abstract.     

液晶分子附着能和盒间隙对响应时间的影响

通过理论分析和实验研究液晶分子附着能和液晶盒间隙对响应时间(τ0)的影响。用液晶盒有效间隙法和表面动力学方程法两种方法推出分析公式,由这两种方法推出的结果是一致的。实验数据与简化方程τ0-dx基本拟合(其中d是液晶盒的间隙,x是指数)。在两种极端的(极大或极小)附着能极限下,指数x分别接近2和1。这个结论有助于优化液晶显示器件的应用。     

Higher-order radiative perturbation theory

As a computationally effective tool, the first-order term of the radiative perturbation theory has been computed successfully, and has been applied in a number of areas. In this article, we develop the computational expressions for the higher-order terms of the perturbation expansion in a plane parallel atmosphere. These expressions are then implemented, and numerical results for some typical cases are presented. These results indicate that the computation is successful and that the higher-order terms are essential in cases where the first-order term alone cannot predict the perturbation with sufficient accuracy.     

Über Sesquiselenide der Lanthanoide: Einkristalle von Ce2Se3 im C‐, Gd2Se3 im U‐ und Lu2Se3 im Z‐Typ

On Sesquiselenides of the Lanthanoids: Single Crystals of C‐type Ce₂Se₃, U‐type Gd₂Se₃, and Z‐type Lu₂Se₃ Single crystals of lanthanoid sesquiselenides (M₂Se₃; here: M = Ce, Gd, Lu) are accessible through conversion of the elements (lanthanoid and selenium) in molar ratios of 2:3 within seven days at 850 °C from evacuated silica ampoules if equimolar amounts of NaCl serve as a flux. In the case of Ce₂Se₃ (a = 897.74(6) pm) und Gd₂Se₃ (a = 872.56(5) pm) the cubic C‐type (I4¯3d, Z = 5.333) forms as dark red beads, whereas the orthorhombic Z‐type (Fddd, Z = 16) emerges for Lu₂Se₃ (a = 1125.1(1), b = 798.06(8), c = 2387.7(2) pm) as orange‐yellow bricks. Upon oxidation of monochloride hydrides (MClH_x or A_yMClH_x; M = Ce, Gd, Lu; x = 1; A = Li, Na; y = 0.5) with selenium in arc‐welded tantalum ampoules the same main products appear with C‐Ce₂Se₃ and Z‐Lu₂Se₃, even with a surplus of NaCl or LiCl as fluxing agent. In the case of Gd₂Se₃, however, black‐red needles of the orthorhombic U‐type (Pnma, Z = 4; a = 1118.2(1), b = 403.48(4); c = 1097.1(1) pm) are yielded instead of C‐Gd₂Se₃. C‐Ce₂Se₃ crystallizes in a cation‐deficient Th₃P₄‐type structure (Ce₂S₃ type) according to Ce_2.667□_0.333Se₄ (Z = 4) or with Z = 5.333 for the empirical formula Ce₂Se₃. Here, Ce³⁺ is coordinated by eight Se^2— anions trigon‐dodecahedrally. In U‐Gd₂Se₃ (U₂S₃ type) two crystallographically independent Gd³⁺ cations with coordination numbers of 7 (Gd1) and 7+1 (Gd2), respectively, are present, exhibiting mono‐ or bicapped trigonal prisms as coordination polyhedra. The crystal structure of Z‐Lu₂Se₃ (Sc₂S₃ type) shows two different Lu³⁺ cations as well, which now both reside in octahedral coordination of six Se^2— anions each.     

Profinite groups of finite cohomological dimension

Let 1→N→G→G/N→1 be a short exact sequence of profinite groups, and let p be a prime number. We prove that if G is of finite cohomological p-dimension n:=cd_p(G)<∞ and if the order of $\text{H}{}^{\mathrm{k}}\text{(N,}\text{F}{}_{\mathrm{p}}\text{)}$ is finite for k:=cd_p(N), the virtual cohomological p-dimension of G/N equals n?k. To cite this article: T. Weigel, P. Zalesskii, C. R. Acad. Sci. Paris, Ser. I 338 (2004).     

2,4,6‐Trifluoropyrimidine. Reactions with nitrogen nucleophiles

In a continuation of our studies involving the nucleophilic displacement of one of the chlorines from 2,4,6‐trichloropyrimidine, we now report the initial displacement of one of the fluorine atoms from 2,4,6‐trifluoropyrimidine using both aliphatic and aromatic amines. The monosubstitution products favor 2‐substitution with ammonia and ethanolamine while aniline gave the 4‐substituted derivative as the preferred product.