Mechanism of Interaction of γ-Halogenated Salts of Pyrylium and Benzopyrylium with Aromatic Amines

Stoichiometry and kinetics of reactions of 2,6-diphenyl-4-chloropyrylium, 4-chloroflavylium, 4-bromoflavylium, and 4-iodoflavylium perchlorates with nucleophiles N,N-dimethylaniline and n-phenylenediamine are studied using cyclic voltammetry and spectroscopy. Nucleophilic substitution in these compounds proceeds via the formation of a charge-transfer complex, which converts into a radical ion pair as a result of the electron transfer. Heterolytic clevage of the C–Hal bond occurs at the stage of pyranyl (flavanyl) radical.     

Ab Initio Structure/Reactivity Investigations of Illudin‐Based Antitumor Agents: A Model for Reaction in vivo

(Hydroxymethyl)acylfulvene (HMAF, irofulven; 4 ), a third‐generation derivative of a natural product extracted from the mushroom Omphalotus illudens, is selectively toxic towards certain forms of malignant tumors. Conversion of HMAF and cognates to stable aromatic derivatives is triggered by thiol attack in vitro and in vivo. Quantum‐chemical methods predict well the structure for several functionalized derivatives of irofulven as compared to known X‐ray crystallographic structures. Computational reaction profiles for thiol attack and aromatic rearrangement of irofulven and illudin S, a toxin from which irofulven is derived, provide insight into HMAF's selectivity and toxicity. Methods used include hybrid density‐functional theory (HDFT), Hartree? Fock (HF), and Møller? Plesset second‐order perturbation theory (MP2). Solvent effects have been explored by means of the new continuum‐solvation method, COSab, presented in an accompanying paper.     

The Computable Dimension of I-Trees of Infinite Height

We study computable trees with distinguished initial subtree (briefly, I-trees). It is proved that all I-trees of infinite height are computably categorical, and moreover, they all have effectively infinite computable dimension.     

Effect of the Structure of Oxypropylated Hydroxyl-Containing Molecules on Glycolysis of Foamed Polyurethane

The activity of a polyether derived from ethylene and propylene oxides (Laprol 5003) and of N,N,N',N'-tetra(hydroxypropyl)ethylenediamine (Lapramol 294) in glycolytic degradation of elastic foamed polyurethane was studied.     

Potts model on complex networks

We consider the general p-state Potts model on random networks with a given degree distribution (random Bethe lattices). We find the effect of the suppression of a first order phase transition in this model when the degree distribution of the network is fat-tailed, that is, in more precise terms, when the second moment of the distribution diverges. In this situation the transition is continuous and of infinite order, and size effect is anomalously strong. In particular, in the case of p = 1, we arrive at the exact solution, which coincides with the known solution of the percolation problem on these networks.Received: 3 December 2003, Published online: 17 February 2004PACS: 05.10.-a Computational methods in statistical physics and nonlinear dynamics - 05.40.-a Fluctuation phenomena, random processes, noise, and Brownian motion - 05.50. + q Lattice theory and statistics (Ising, Potts, etc.) - 87.18.Sn Neural networks