X-ray structure and UV spectroscopic studies of (adenmato-N9)triethylphosphinegold(I)

The preparation, characterization, and X-ray structure analysis of (adeninatoN9)triethylphosphinegold(I) is reported. The crystal structure consists of discrete molecules, the adeninate anion coordinates via the N(9) atom with a Au-N(9) bond distance of 2.057(5) Å and the linear geometry about the Au atom is completed by the P atom of a disordered Et₃P ligand; the Au-P(1) bond distance is 2.238(2) Å and the N(9)-Au-P(1) bond angle is 178.8(2)°. The crystals are orthorhombic, space groupPbca, with unit cell dimensionsa=8.528(1),b=17.797(3),c=18.526(2) Å andZ=8. The structure was refined by a full-matrix least-squares procedure to finalR=0.030 andR _w =0.033 for 1749 reflections withI>2.5a(I). The electronic spectrum of the complex dissolved in water in the near ultraviolet is consistent with essentially separate -electron systems of the adenine and phosphinegold moieties; a conclusion which corroborates the X-ray structural results.     

Synthesis of 3-formyltetronic acid and enamine derivatives

The first reported synthesis of 3-formyltetronic acid and its conversion to enamine derivatives is described. 3-Dimethylaminomethylene-2,4-dioxotetrahydrofuran derivatives were also prepared by treatment of tetronic acids with dimethylformamide diethyl acetal. Nmr spectral studies are included.     

The search for a new model structure of β-Factor XIIa

We present the search for a new model of -factor XIIa, a blood coagulation enzyme, with an unknown experimental 3D-structure. We decided to build not one but three different models using different homologous proteins as well as different techniques and different modellers. Additional studies, including extensive molecular dynamics simulations on the solvated state, allowed us to draw several conclusions concerning homology modelling, in general, and -factor XIIa, in particular.     

(1-Adamantanethio)pyridines and tetrahydropyridines from the reaction of 1-adamantanethiol with pyridine I-oxide in acetic anhydride

The reaction of pyridine 1-oxide with 1-adamantanethiol in acetic anhydride produced a mixture of 2- and 3-(1-adamantanethio)pyridines, 1-aeetyl-2-(1-adamantanethio)-3-hydroxy-4-acetoxy-1,2,3,4-telrahydropyridine and the corresponding 3-acetoxyderivative. Pure substances were separated by means of column chromatography on alumina. The tetrahydropyridines were identified by means of their proton magnetic and mass spectra. 4-(1-Adamantanethio)pyridine was synthesized from 4-chloropyridinc and 1-adamantanethiol. The three isomeric (1-adamantanethio)-pyridines were, each, cleaved by concentrated hydrochloric acid to give 1-chloroadamantane and the corresponding pyridinethiol.     

Role of pyridine in the catalytic activation of sodium hypochlorite in the presence of manganese porphyrin

Steric and electronic influences of various substituted pyridines support the hypothesis of the coordination of pyridine in the manganese porphyrin-catalysed epoxidation of olefins with sodium hypochlorite solution.     

Calculation of Franck-Condon factors including anharmonicity: simulation of the C2H4+X2B3u<--C2H4X1A(g) band in the photoelectron spectrum of ethylene

Our new simple method for calculating accurate Franck-Condon factors including nondiagonal (i.e., mode-mode) anharmonic coupling is used to simulate the C2H4+X2B3u<--C2H4X1A(g) band in the photoelectron spectrum. An improved vibrational basis set truncation algorithm, which permits very efficient computations, is employed. Because the torsional mode is highly anharmonic it is separated from the other modes and treated exactly. All other modes are treated through the second-order perturbation theory. The perturbation-theory corrections are significant and lead to a good agreement with experiment, although the separability assumption for torsion causes the C2D4 results to be not as good as those for C2H4. A variational formulation to overcome this circumstance, and deal with large anharmonicities in general, is suggested.