Synthesis and characterization of novel "3 + 2" oxorhenium complexes, ReO[SNO][NN

The present paper deals with the synthesis and structural characterization of novel neutral oxorhenium(V) complexes of the general formula ReO[SNO][NN]. The simultaneous action of the tridentate SNO ligand, N-(2-mercaptoacetyl)glycine (1), and the bidentate NN ligand, N-phenylpyridine-2-aldimine (2), on ReOCl3(PPh3)2 leads to the formation of two isomers 4a and 4b of the general formula ReO[SNO][NN], as a result of the different orientations of the NN ligand. In both cases, the SNO donor atoms of the tridentate ligand occupy the three positions in the equatorial plane of the distorted octahedron, whereas the oxo group is always directed toward one of the apical positions. In the first isomer, 4a, the imino nitrogen of the NN ligand occupies the fourth equatorial position and the pyridine type nitrogen is directed trans to the oxo group, while in the second isomer, 4b, the imino nitrogen of the NN ligand occupies the apical position trans to the oxo group and the pyridine type nitrogen completes the equatorial plane of the distorted octahedron. The [SNO][NN] mixed-ligand system was applied in the synthesis of the oxorhenium complex 5 in which the 1-(2-methoxyphenyl)piperazine moiety, a fragment of the true 5-HT1A antagonist WAY 100635, has been incorporated in the NN bidentate ligand (NN is N-{3-[4-(2-methoxyphenyl)piperazin-1-yl]propyl}pyridine-2-aldimine). In this case, high-performance liquid chromatography and NMR showed the existence of one isomer, 5, in which the pyridine nitrogen is trans to the oxo core, as demonstrated by crystal structure analysis.     

Über die Synthese und die Eigenschaften von 1,2,4,5-Tetrazinen, 2. Mitt.

Zusammenfassung Die Behandlung von Thiazol-2- und 6-Acetamino-pyridin-3-nitril mit Hydrazinhydrat führt zu den entsprechenden 3,6-disubstituierten 1,2-Dihydro-1,2,4,5-tetrazinen. Versuche, unter den gleichen Bedingungen die Synthese des 1,2-Dihydrotetrazins aus p-Methoxy-benzylcyanid zu verwirklichen, lieferten ausschließlich das 3,5-disubstituierte 4-Amino-1,2,4-triazol.1. Mitt.:F. Dallacker, Mh. Chem.91, 294 (1960).     

Automated phenylthiocarbamyl amino acid analysis of carboxypeptidase/aminopeptidase digests and acid hydrolysates

A fully automated exopeptidase digestion procedure for the partial determination of N- and C-terminal peptide/protein sequence is described. The digestion of various substrates with aminopeptidase M, carboxypeptidase A, P or Y was accomplished with the Varian 9090 autosampler's robotic automix routines. The released free amino acids, in addition to free amino acids from acid hydrolysates, were derivatized with phenylisothiocyanate in an automated fashion and subsequently chromatographed on a C18 column for separation and quantitation. The advantages of automating this precolumn phenylisothiocyanate derivatization are the virtual elimination of sample manipulation errors and very reproducible data due to the precise control of the reaction conditions both of which, facilitate the interpretation of the exopeptidase reaction kinetic data.     

Molecular dynamics in nanostructured polyimide-silica hybrid materials and their thermal stability

Molecular motion and thermal stability in two series of nanophase-separated polyimide-silica (PI-SiO₂) hybrid networks with chemically bound components were studied. The hybrids were prepared via a sol-gel process and differed in PI structure and chain length, and in SiO₂ content ranging from 10 to 50 wt.%. Differential scanning calorimetry, laser-interferometric creep rate spectroscopy, dielectric relaxation spectroscopy, thermally stimulated depolarization current techniques, and thermogravimetry were used covering, on the whole, the ranges of 100–900 K and 10⁻³-10⁹ Hz. Silica domains influenced PI dynamics in two opposite directions. Loosened segmental packing in chains confined to nanovolumes resulted mainly in rise of small-scale motion below β-relaxation region, while anchoring of chain ends to ‘rigid walls’ caused, contrarily, a partial or total suppression of segmental motion above T_β, especially drastically at the temperatures close to and within glass transition. The latter resulted in a large change in thermal stability, e.g., 2.5-fold increasing of the apparent activation energy of thermooxidative degradation, and more than 100° rise of predicted long-term thermal stability for the hybrids as compared to that for PI.     

On the relative homology of cleft extensions of rings and abelian categories

We study the relative homological behaviour of the omnipresent class of cleft extensions of abelian categories. This class of extensions is a natural generalization of the trivial extensions studied in detail by Fossum, Griffith and Reiten and by Palmer and Roos. We apply our results to the relative homology of cleft extensions of rings.     

Asymptotic packing and the random greedy algorithm

Let H be an r-uniform hypergraph satisfying deg(x) = D(1 + o(1)) for each vertex xϵ V(H) and deg(x, y) = o(D) for each pair of vertices x, y ϵ V(H), where D → infinity. Recently, J. Spencer [5] showed, using a branching process approach, that almost surely the random greedy algorithm finds a packing of size at least n/r(1 − o(1)) for this class of hypergraphs. In this paper, we show an alternative proof of this via “nibbles.” Further, let T_α be the number of edges that the random greedy algorithm has to consider before yielding a packing of size [n/r · (1 − α)]. We show that almost surely T_α ∼ (1/α)^r−1 · n/r(r − 1) as α → 0⁺ holds. © 1996 John Wiley & Sons, Inc.