Chemometric approaches in environmental problems concerning PCDD and PCDF. Data interpretation and source correlation. Mechanisms of formation and destruction in MSW combustion process

Summary The role of multivariate analysis methods in evaluating, rationalizing, and working out complex environmental problems is discussed. The discussion is organized in two sections; a literature analysis of the application of chemometric methods to PCDD/PCDF data interpretation and source correlation and a review of the role of chemometric methods in analysing the results obtained by the Authors studying PCDD/PCDF formation and destruction mechanisms in MSW combustion processes.     

Accurate redetermination of the X-ray structure and electronic bonding in adenosylcobalamin

The electronic structure of adenosylcobalamin (B12 coenzyme, AdoCbl) has been calculated by a density functional method, using the orthogonalized linear combination of the atomic orbital method (OLCAO). Since a fixed accurately determined geometry was needed in such calculations, the crystal structure of adenosylcobalamin has been redone and refined to R = 0.065, using synchrotron diffraction data. Comparison with the recently reported electronic structures of cyano- (CNCbl) and methylcobalamin (MeCbl) shows that the net charges and bond orders vary only on the axial donors. The values in the three cobalamins suggest that the Co-C bond in MeCbl has a strength similar to that in AdoCbl, but it is significantly weaker that that in CNCbl. Present results are compared with those previously reported for the analogous corrin derivatives; i.e., simplified cobalamins with the side chains a-f replaced by H atoms. Despite a qualitative agreement, a discrepancy in the calculated HOMO-LUMO gap is found.     

Nonlinear forecasting and iterated function systems

The theory of dynamical forecasting can be extended to iterated function systems. An unordered set of iterates may be sufficient to construct a simulation of the unknown dynamics. The underlying dynamical system may be nondeterministic: A random element may be allowed in the dynamics, and retrieved by our proposed procedures. A first application of these extensions pertains to the reconstruction of fractal attractors, and allows us to solve the so-called inverse problem in Iterated Functions Systems.     

A ketogenic diet increases succinic dehydrogenase (SDH) activity and recovers age-related decrease in numeric density of SDH-positive mitochondria in cerebellar Purkinje cells of late-adult rats

Ketogenic diets (KDs) have been applied in the therapy of paediatric epilepsy for nearly a century. Recently, beneficial results have also been reported on metabolic disorders and neurodegeneration, designating aged individuals as possible recipients. However, KDs efficacy decrease after the suckling period, and very little is known about their impact on the aging brain. In the present study, the effect on the neuronal energetic supply of a KD containing 20% of medium chain triglycerides (MCT) was investigated in Purkinje cells of the cerebellar vermis of late-adult (19-month-old) rats. The animals were fed with the KD for 8 weeks, and succinic dehydrogenase (SDH) activity was cytochemically determined. The following parameters of SDH-positive mitochondria were evaluated by the use of a computer-assisted image analysis system connected to a transmission electron microscope: numeric density (Nv), average volume (V), volume density (Vv), and cytochemical precipitate area/mitochondrial area (R). Young, age-matched, and old animals fed with a standard chow were used as controls. We found significantly higher Nv in MCT-KD-fed rats vs. all the control groups, in young vs. late-adult and old controls, and in late-adult vs. old controls. V and Vv showed no significant differences among the groups. R was significantly higher in MCT-KD-fed rats vs. all the control animals, and in old vs. young and late-adult controls. Present data indicate that the ketogenic treatment counteracted age-related decrease in numeric density of SDH-positive mitochondria, and enhanced their metabolic efficiency. Given the central role of mitochondrial impairment in age-related physio-pathological changes of the brain, these findings may represent a starting point to examine novel potentialities for KDs.     

The spectroscopy of surface vibrations by atom scattering

The recent progress in the production of highly monochromatic atomic beams is opening new perspectives in surface physics, having paved the way for a full determination of the surface vibrational structure. After a discussion on the possible determination of Rayleigh wave dispersion curves from angular distributions exploiting the kinematical focussing effect, a short review is presented on the direct measurement of surface phonon dispersion curves, first achieved by Brusdeylins, Doak and Toennies in alkali halides, from time-of-flight (TOF) spectra of scattered He atoms. A comparison is made with the existing theories of surface phonons in ionic crystals. The state of the art in the theory of inelastic processes is briefly illustrated in order to discuss the theoretical interpretation of TOF spectra. The one-phonon energy loss spectra of He scattering from LiF(001) calculated for a hard corrugated surface model are found to be in general good agreement with the experimental TOF spectra. From such a comparison evidence is obtained that: i) one-phonon processes are predominant, and ii) in addition to Rayleigh waves important contributions to the inelastic scattering come from the surface-projected density of bulk phonons. Important effects due to inelastic resonances with surface bound states are put in evidence and explained by simple kinematical arguments. The possible observation of surface optical modes in NaF(001) is finally discussed.     

Reactivity of β-aluminas with water

The reactivity with air moisture of finely divided crystals of Na β and Li⁺-containing β-aluminas is analyzed with thermogravimetric and X-ray techniques. For Na β-alumina two distinct water intake processes are evident: 1) a fast one, controlled by the elastic interactions among water molecules near the crystal boundaries; 2) a slow one, driven by water diffusion away from the boundaries. For finely divided crystals of Li β-alumina the two processes cannot be distinguished but the slow one is observable in crystals of macroscopic dimensions. The water intake is generally accompanied by an expansion of the c-axis. However, the relationship between water content and c-parameter is highly non-linear and the c-axis length at room temperature depends upon the thermal history of the sample. Our results confirm previous reports suggesting that β-aluminas absorb about one water molecule per cation of the conducting plane.     

GSI anomaly and spin–rotation coupling

We propose a model in which a recently reported modulation in the decay of the hydrogenlike ions ¹⁴⁰Pr⁵⁸⁺, ¹⁴²Pm⁶⁰⁺ and ¹²²I⁵²⁺ arises from the coupling of rotation to the spin of electron and nucleus. The model shows that the spin–spin coupling of electron and nucleus does not contribute to the modulation and predicts that the anomaly cannot be observed if the motion of the ions is rectilinear, or if the ions are stopped in a target. It also supports the notion that the modulation frequency is proportional to the inverse of the atomic mass and that no modulation is expected for the β⁺${\beta }^{+}$-decay. The model predicts that for He-like ions the modulation is still present.     

A complete treatment of a steady-state four-level model for the interpretation of OH laser-induced fluorescence measurements in atmospheric pressure flames

In order to obtain OH concentration measurements in atmospheric pressure flames from saturated fluorescence signal, we have developed a stationary four-level model. A general relationship between the measured upper state population and the total number density has been derived. The effects of the imbalance between the rotational transfer rates in the upper and ground states is analyzed. We show that in the case of comparable rotational rates, the results of our treatment are similar to the ones obtained with the balanced cross rate model. A set of complementary data which should facilitate absolute OH concentration measurements is also pointed out.