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.     

The Theory of Kairons

In relativistic quantum mechanics wave functions of particles satisfy field equations that have initial data on a space-like hypersurface. We propose a dual field theory of “wavicles” that have their initial data on a time-like worldline. Propagation of such fields is superluminal, even though the Hilbert space of the solutions carries a unitary representation of the Poincaré group of mass zero. We call the objects described by these field equations “Kairons”. The paper builds the field equations in a general relativistic framework, allowing for a torsion. Kairon fields are section of a vector bundle over space-time. The bundle has infinite-dimensional fibres.     

Ultrafast dynamics of metal complexes of tetrasulphonated phthalocyanines

A promising material in medicine, electronics, optoelectronics, electrochemistry, catalysis, and photophysics, tetrasulphonated aluminum phthalocyanine (AlPcS(4)), is investigated by means of steady-state and time-resolved pump-probe spectroscopies. Absorption and steady-state fluorescence spectroscopy indicate that AlPcS(4) is essentially monomeric. Spectrally resolved pump-probe data are recorded on time scales ranging from femtoseconds to nanoseconds. The nature of these fast processes and pathways of the competing relaxation processes from the initially excited electronic states in aqueous and organic (dimethyl sulfoxide) solutions are discussed. The decays and bleaching recovery have been fitted in the ultrafast window (0-10 ps) and later time window extending to nanoseconds (0-1 ns). While the excited-state dynamics have been found to be sensitive to the solvent environment, we were able to show that the fast dynamics is described by three time constants in the ranges of 115-500 fs, 2-25 ps, and 150-500 ps. We were able to ascribe these three time constants to different processes. The shortest time constants have been assigned to vibrational wavepacket dynamics. The few picosecond components have been assigned to vibrational relaxation in the excited electronic states. Finally, the 150-500 ps components represent the decay from S(1) to the ground state. The experimental and theoretical treatment proposed in this paper provides a basis for a substantial revision of the commonly accepted interpretation of the Soret transition (B transition) that exists in the literature.     

Numerical simulation of two-stage combustion in SI engine with prechamber

Burning lean mixture in spark ignition (SI) engine leads to decrease in temperature of combustion process and is one of the methods of limiting nitric oxide emission and increasing the engine efficiency. The two-stage combustion system of stratified mixture (engine with prechamber) can be an effective method of lean mixture combustion. The paper presents the results of three-dimensional modeling of fuel mixture preparation and combustion in SI engine with sectional combustion chamber powered by liquefied fuel. Three dimensional modeling was performed in KIVA-3V code. The modeling results were compared with results obtained from the analysis of experimental measurements of two-stage combustion test engine operating at the Institute of Internal Combustion Engines and Control Engineering (Czestochowa University of Technology). The performed simulations of the combustion process provided data concerning the spatial and temporal distributions of turbulent kinetic energy, pressure, temperature and nitric oxides concentration in the combustion chambers of the engine. The engine model with two-stage combustion system properly represents the real processes which occur in the combustion chambers of the test engine. Pressure and temperature courses in function of CA obtained from the experiment and modeling were in good qualitative and quantitative consistence. Comparison of modeled and measured nitric oxide emissions revealed relatively significant discrepancies. In case of λ = 1.4, the measured values of NO_x concentration were 1.75 times higher than the modeled values. In case of λ = 2.0, the modeled and measured values were close to each other and were within the range of measurement error.     

Application of semi-permeable membrane dialysis/ion trap mass spectrometry technique to determine polybrominated diphenyl ethers and polychlorinated biphenyls in milk fat

Polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) are hazardous food contaminants, their maximum legally allowable levels in food and environment are in the low pg g⁻¹ range. Therefore some highly selective and sensitive analytical methods must be used to determine them. The 96/23/EC Directive implemented by EC Decision of 12 August 2002 requires recovery rate of an analyte at a concentration below 1 ng g⁻¹ within the 50–120% range at relative standard deviation (RSD) as low as possible.