GEOMETRY OF INTERCALATION OF PSORALENS IN DNA APPROACHED BY MOLECULAR MECHANICS*

The results of molecular mechanical calculations on intercalation complexes of 3-carbethoxypsoralen, 5-methoxypsoralen, 8-methoxypsoralen, 7-methylpyrido[3,4-c]psoralen (MepyPs) and 7-methylpyrido[4,3-c]psoralen (2N-MePyPs) with the double stranded duodecanucleotide d(CGCGATATCGCG)2 are presented. In the energy-minimized structures, the psoralens are intercalated with their plane orthogonal to the helix axis. Stacking interactions between the furan ring of the psoralen and the adjacent bases are maximized in most derivatives studied, whereas the effect of the various substituents of the psoralen ring is to specifically push part of the molecule towards either the minor or the major groove, preventing a symmetrical intercalation (with respect to the two strands of the DNA). The relative position of the psoralen ring and of the adjacent thymine foreshadows the formation of furan-side monoadducts in 3-CPs, MePyPs and 2N-MePyPs, whereas the formation of a pyrone-side monoadduct appears as geometrically more favourable in 5-MOP and both furan- and pyrone-side monoadducts can be geometrically envisaged in 8-MOP. A good correlation therefore exists between the more or less favourable equilibrium geometries and the experimentally observed photoreactions. The present study is the first attempt to characterize the geometrical parameters as part of a complex set of geometrical, dynamical and excited state parameters governing the overall DNA-psoralen photoreaction.     

On the role of dissociative ionization in the formation of argon dimer ions

The formation of Ar ₂ ⁺ ions has been investigated by means of the threshold photoelectron photoion coincidence (TPEPICO) technique. Two pathways for the formation of Ar ₂ ⁺ ions are important. One is a direct path via excitation of Rydberg states of Ar₂ with consecutive autoionization. The other path is dissociative ionization of larger argon clusters, in this case argon trimers. These two pathways lead to Ar ₂ ⁺ ions with different internal energy. The pathways are easily distinguished in the TPEPICO-TOF spectra by the kinetic energy released (KER) in the dissociative ionization. The KER for the reaction Ar ₃ ⁺ → Ar ₂ ⁺ + Ar was measured as a function of the photon energy and compared to the KER expected from statistical theory. The agreement is satisfying and confirms that Ar ₃ ⁺ ions do indeed dissociate at the thermochemical threshold. At higher photon energy the excited²Π(3/2)g state of Ar ₃ ⁺ is also detected from a second component in the KER. By applying a kinetic energy discrimination it is possible to measure cluster ion spectra in the presence of larger clusters but essentially without interference from the latter.     

Monte Carlo renormalization of hard sphere polymer chains in two to five dimensions

A renormalization group for polymer chains with hard-core interaction is considered, where a chain ofN ₀ links of lengthl ₀ and hard-core diameterh ₀ is mapped onto a chain ofN ₁=N ₀/s links of lengthl ₁ and hard-core diameterh ₁. The lengthl ₁ is defined in terms of suitable interior distances of the original chain, andh ₁ is found from the condition that the end-to-end distance is left invariant. This renormalization group procedure is carried through by various Monte-Carlo methods (simple sampling is found advantageous for short enough chains or high dimensionalities, while dynamic methods involving kinkjumps or reptation are used else). Particular attention is paid to investigate systematic errors of the method by checking the dependence of the results on bothN ₀ ands. It is found that for dimensionalitiesd=2, 3 only the nontrivial fixed-point is stable, where upon iteration the ratio _k =h _k /l _k tends to nonzero fixed-point value ^*, while ford=4,5 the method converges to the gaussian fixed point with ^*=0. Taking both statistical and systematic errors into account, we estimate the exponentv asv=0.74±0.01 (d=2) andv =0.59±0.01 (d=3). The results are consistent with the expected crossover exponents =1/2 (d=3) and =1 (d=2), respectively.     

Catalytic partial oxidation of hydrogen sulfide on chabazite tuff

The catalytic activity of a chabazite tuff in the partial oxidation of H₂S to sulfur has been determined. The effects of temperature, feed concentration and chemical composition of the tuff on H₂S conversion and selectivity to sulfur have been investigated. Encouraging results in view of a possible use in H₂S removal processes have been obtained.

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