Properties of the skeleton of aggregates grown on a Cayley tree

We discuss and analyze a family of trees grown on a Cayley tree, that allows for a variable exponent in the expression for the mass as a function of chemical distance, M(l)l ^dl . For the suggested model, the corresponding exponent for the mass of the skeleton,d _l ^s , can be expressed in terms ofd _l asd _l ^s = 1,d _l d _l ^c = 2;d _l ^s = d _l –1,d ₁ d _l ^c = 2, which implies that the tree is finitely ramified ford _l 2 and infinitely ramified whend _l 2. Our results are derived using a recursion relation that takes advantage of the one-dimensional nature of the problem. We also present results for the diffusion exponents and probability of return to the origin of a random walk on these trees.     

On the separation of initial and final state effects in photoelectron spectroscopy using an extension of the auger-parameter concept

First, we show that the quantity Δβ(i) = ΔE_A(kii) + 2ΔE_B(i) — ΔE_B(k) is directly related to the final state relaxation contribution ΔE_R(i) of the binding energy shift ΔE_B(i). ΔE_A(kii) is the kinetic energy shift of the Auger transition which corresponds to the decay of a hole state with a hole in level k into a final state with two holes in level i. The shift parameter Δβ(i), which is based on information on two binding energies, is conceptually similar to Wagner's Auger parameter. To establish the relation between Δβ(i) and ΔR(i) one needs, however, less drastic approximations than in the case of Auger parameter shifts. The only approximation necessary is the assumption that ΔR(i) is determined by coulomb contributions.Secondly, we use Δβ (i) to analyse the experimental data of eighteen gaseous phosphorus-containing compounds obtained by Sodhi and Cavell¹. It is shown that ΔR(P_2p) is strongly related to changes in the polarizability of the ligands. The initial state effects derived from our study deviate from those expected on the basis of simple electronegativity considerations.     

A Direct Asymmetric Synthesis of Juglomycin A

Juglomycin A has been synthesized in four steps from 5-methoxy-1-naphthol.     

Complexing effects in the solvent extraction of thallium(I) 2-mercaptobenzothiazole

Studies of the extraction of thallum(l) from aqueous solution in the absence and presence of aqueous complexing agents into chloroform containing 2-mercaptobenzothiazole are described. Fluoride, chloride, bromide, iodide, thiocyanair, cyanide, and sulfate were employed as aqueous complexing agents. A number of the participating species were identified and association constants are estimated.     

Synthesis and modeling study of (2S,5R,6R)- and (2S,5R,6S)-6-hydroxy- 8-(1-decynyl)-benzolactam-V8 as protein kinase C modulators

[structures: see text] Both (2S,5R,6R)- and (2S,5R,6S)-6-hydroxy-8-(1-decynyl)benzolactam-V8 were designed and synthesized as PKC modulators. Biological assays reveal the (6R)-ligand to be 20-fold more potent than its (6S)-counterpart in binding to PKC alpha.     

Copper(II) complexes of tetrapeptides containing cysteinyl and histidinyl residues

It is becoming increasingly apparent that the coordination chemistry of oligopeptides with Cys-X-Y-Cys and His-X-Y-Cys sequences (X, Y = variable amino acid residues) is an important theme in transition metal and bioinorganic chemistry(1,2). The Cys-X-Y-Cys sequence is often encountered in the metal binding site of several metalloproteins, such as iron–sulfur proteins, e.g. rubredoxins(3) and ferrodoxins(4), high potential iron–sulfur proteins(5), metallothioneins(6), zinc proteins(7) etc. The amino acid sequence His-X-Y-Cys is also of bioinorganic importance since it has been found in the active site of copper(8), iron–sulfur(9) and zinc(10) proteins. We are currently seeking to develop the area of transition metal/Cys-X-Y-Cys and His-X-Y-Cys peptide interactions(11,12); our goals are: (i) to elucidate the role of these sequences in the biological activity and mechanism of action of the above metallobiomolecules, and (ii) to find possible new and more effective agents for the elimination of heavy metals from the human organism or from contaminated waste waters. Here we report the preparation and preliminary characterization of copper(II) complexes of tetrapeptide ligands containing the Cys-X-Y-Cys and His-X-Y-Cys sequences. This revised version was published online in June 2006 with corrections to the Cover Date.     

Synthesis of the methanesulfonates of α-(4-chlorophenyl)-α-[1-(2-chlorophenyl)emenyl]-1H-1,2,4-triazole-1-ethanol and α-[1-(2-chlorophenyl)ethenyl]-α-(2,4-difluorophenyl)-1H-1,2,4-triazole-1-ethanol,alpha styryl carbinol antifungal agents

The methanesulfonates of (α-(4-chlorophenyl)-α-[1-(2-chlorophenyl)ethenyl]-1H-1,2,4-triazole-1-ethanol and α-[1-(2-chlorophenyl)ethenyl]-α-(2,4-difluorophenyl)-1H-1,2,4-triazole-1-ethanol ( 1a, b ) are orally effective α-styryl carbinol derivatives developed for the treatment and prevention of systemic fungal infections. Practical new processes amenable for the large-scale production of these compounds are described. Of note is the selection of dichlorostyrene as a convenient precursor of the styryl portion, modification of a sensitive Grignard addition into a realistic preparative reaction and the use of 1,2,4-triazole simultaneously as a base transfer agent and nucleophile.     

Electron energy level crossings in the time-dependent Born-Oppenheimer approximation

Summary We summarize the results of a mathematical study of the time-dependent Born-Oppenheimer approximation near crossings of two non-degenerate electron energy surfaces. We illustrate our techniques by relatively simple examples that contain the essential ingredients of the general cases. We discuss all generic types of crossings of two non-degenerate electron energy surfaces.Supported in part by the National Science Foundation under Grant number DMS-8801360