Submicron particles removal by charged sprays. Fundamentals

New regulations regarding the PM1 emission by power plants and transport vehicles require novel technical solutions for the abatement of particulate matter emission in submicron size range. Particles of this size are difficult to remove by conventional methods, and therefore various variants of wet electrostatic scrubbers have been developed. In such devices, the electrostatic forces between charged particles and collectors (water droplets) are used to permanently remove them from the gas. The paper focuses on the state-of-the-art of wet electrostatic scrubbing technique used for the removal of submicron particulate matter from exhaust gases with particular emphasis upon marine Diesel engines.     

Circular dichroism and conformational dynamics of cephams and their carba and oxa analogues

The biological activity of bicyclic beta-lactam antibiotics depends strongly on the absolute configuration of the bridgehead carbon atom. Frelek and co-workers proposed an empirical helicity rule relating the configuration of the bridgehead carbon atom to the sign of the 220 nm band in the electronic circular dichroism (CD) spectrum of beta-lactams. Here we use synthetic organic chemistry, CD spectroscopy, and time-dependent density functional theory (TDDFT) to investigate the validity of this structure-property relationship for eight model compounds. For conformationally flexible beta-lactams, substantial thermal effects are found which must be included in calculations. To this end, we combine TDDFT calculations of CD with full quantum-mechanical Born-Oppenheimer molecular dynamics (MD) simulations for the first time. The CD spectra are sampled with ground-state density functional trajectories of up to 60 ps. The MD simulations show a surprisingly high sensitivity of the CD to the molecular conformation. On the other hand, the relation between CD and thermally averaged structural parameters is much less complex. While the helicity rule does not seem to hold for individual conformers, it is confirmed by the calculations for seven out of eight systems studied if thermally averaged CD spectra and structures are considered. Since thermal effects on CD can be larger than typical inherent inaccuracies of TDDFT, our results emphasize the need for a systematic treatment of conformational dynamics in CD calculations even for moderately flexible systems. Temperature-dependent CD measurements are very useful for this purpose. Our results also suggest that CD spectroscopy may be used as a sensitive probe of conformational dynamics if combined with electronic structure calculations.     

Reaction of 3,3′,4,4′-tetramethyl-1,1′-diphosphaferrocene with [Re2(CO)8(CH3CN)2]: Novel coordination modes of the 1,1′-diphosphaferrocene ligand

Reaction of 3,3′,4,4′-tetramethyl-1,1′-diphosphaferrocene (1) with [Re₂(CO)₈(CH₃CN)₂] afforded two trimetallic complexes in which the heterometallocene is ligated across the Re-Re bond. The structure of the complex having 1 bridging the Re₂(CO)₈ moiety through two P atoms was determined by X-ray diffraction and compared with those of analogous complexes with organic bridging bis-phosphines. The second complex obtained in this reaction presumably contains 1 acting as a (P,Fe) bridging ligand.     

Why are the kinked polyacenes more stable than the straight ones? A topological study and introduction of a new topological index of aromaticity

A topological model for estimating the stability of benzenoid hydrocarbons (BHs) is presented showing an acceptable linear dependence on Hess-Schaad resonance energy per pi-electron values. The topological measure of stability is accessible by use of pencil calculation and is based on counting cis-type fragments of double bonds in all canonical structures of a given BH. Evidence is given that infinite chains of straight linear polyacenes are always less stable than the kinked ones.     

Photochemical and photophysical study on the kinetics of the atmospheric photodissociation of acetone

The pressure dependence of the photodissociation quantum yield of acetone has been determined in different buffer gases at 308 nm. Results by Stern-Volmer analyses are in accordance with a suggested photolysis mechanism. Luminescence spectra, lifetimes and transition dipole moments have been determined. The energy transfer process by O₂ to give O₂(¹Δ_g) is of minor importance in the case of the singlet excited state of acetone, while it is the dominant deactivation process for the triplet state.     

Transition to chaos in the self-excited system with a cubic double well potential and parametric forcing

We examine the Melnikov criterion for a global homoclinic bifurcation and a possible transition to chaos in case of a single degree of freedom nonlinear oscillator with a symmetric double well nonlinear potential. The system was subjected simultaneously to parametric periodic forcing and self-excitation via negative damping term. Detailed numerical studies confirm the analytical predictions and show that transitions from regular to chaotic types of motion are often associated with increasing the energy of an oscillator and its escape from a single well.