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.     

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.     

Improvements to air mass calculations for ground-based infrared measurements

High-resolution ground-based infrared solar spectra are routinely recorded at the Network for the Detection of Stratospheric Change (NDSC) stations. These data sets play a key role in providing a long-term record of atmospheric composition and their links to climate change. The analysis of observed infrared spectra involves comparison to a computer-modeled atmosphere where knowledge of the air mass distribution is an essential component. This note summarises improvements made to an existing and widely used computer code (FSCATM) to perform refractive ray-tracing and calculation of the air mass distribution. Changes were made towards higher vertical resolution in the troposphere and increased numerical precision. The revised FSCATM improves the analysis of infrared spectra mostly through the more accurate representation of the temperature profile. Air mass differences with respect to earlier versions are documented and are typically <0.7%, exceptions being extreme cases of inversion layers. The current version provides ray tracing and air mass calculations for any terrestrial observation site. The output files are reported in a format compatible with the SFIT and SFIT2 retrieval algorithms, which are widely used for NDSC infrared atmospheric studies. The improved computer code, documentation, reference profiles, and test cases are available electronically.     

Sugar conjugates of fulvestrant (ICI 182,780): efficient general procedures for glycosylation of the fulvestrant core

We have prepared glucose and cellobiose conjugates at the phenolic 3- and hydroxylic 17-positions of the pure anti-estrogenic compound fulvestrant (ICI 182,780), which has recently been approved in the USA for the treatment of advanced postmenopausal breast cancer. Glycosylation at the 17-position was achieved most effectively using pivaloyl protection of the sugar imidates employed, which we found suppressed the competing transacylation reaction and led to improved yields of the product glycosides.