Stemmosides C and D, two novel unusual pregnane glycosides from Solenostemma argel: structural elucidation and configurational study by a combined NMR-quantum mechanical strategy

Stemmosides C and D, two novel pregnane glycosides characterized by an unusual C-17 side chain were isolated from the pericarps of Solenostemma argel. In addition, stemmoside D displays an uncommon 14β proton configuration, apparently being the first pregnane isolated from plants known to have a 15 keto, cis CD ring junction. Their structures have been established by ESIMS and NMR experiments. The relative configuration of the molecules was determined using a strategy based on the simulation of ¹H, ¹³C, and J coupling NMR parameters. DFT calculations of ¹H and ¹³C chemical shifts, and of the ¹H homonuclear spin–spin coupling constants were performed with the mPW1PW91 functional using the 6-31G(d,p) basis set on the fully optimized geometries of all the possible stereoisomers.     

On the Spectral Rigidity of Hopf Manifolds

We characterize Hopf manifolds of complex dimension 3 (resp. 2) in the class of compact locally conformal Kaehler manifold ( resp. Hermitian manifold ) by the spectrum of the Laplacian acting on functions.     

Unsteady axisymmetric stagnation flow on a circular cylinder

Unsteady, axisymmetric stagnation flow about a circular cylinderis examined when the far-field flow is a periodic function oftime with a fixed time average and an oscillatory part of prescribedamplitude and frequency. Solutions are computed for arbitraryvalues of the Reynolds number, quantifying the effects of surfacecurvature, and a frequency parameter based on the period ofthe far-field flow. It is found that solutions remain regularand periodic provided that the far-field amplitude lies belowa critical value. Above this value, solutions terminate in afinite-time singularity. The blow-up time is delayed by increasingthe curvature of the surface. These results are corroboratedby asymptotic predictions valid in the limits of small and largeamplitude and frequency. For large Reynolds number, the problemreduces to the two-dimensional stagnation-point flow againsta plane wall studied by previous authors.     

Determination of the unsaturated losses and of the saturation intensity in the KrCl excimer laser

The unsaturated losses , and the saturation intensityI _s, were measured in an uv-preionized KrCl laser for optimized He and Ne based laser gas mixtures. The measurements were made as a function of the specific power loading and of the total pressure of the laser mixtures. Higher values for andI _s were found for the Ne-based laser mixture than for the He-based mixture. At 45 kV charging voltage and at 355 kPa of total pressure we measured =0.053 cm^–1 andI _s =9.4MW/cm² for the Ne based mixture, and =0.035 cm^–1 andI _s =5.1MW/cm² for the He based mixture.     

A boxmodel development to study the relationships between the photo-oxidants and the particles formation in the troposphere

The model BAGS (Boxmodel for Aerosol and Gasphase Simulations) has been developed. It is composed of two major modules: the first one describes the system of the chemical reactions in the gaseous phase, the second one calculates the aerosol chemical composition and the dimensional distribution of the particles. The boxmodel has been developed with the introduction of new chemical and physical processes, not previously included, in particular the formation of Secondary Organic Aerosol. The other implemented processes are a module for the dynamic of the particle population, nucleation, coagulation and dry deposition. The last phase of the work has been a check of the BAGS capabilities by a series of tests, that have permitted to compare it with other models (MAPS and MADM). The tests in particular have concerned the aerosol water content prediction, the photochemistry, the condensation of the inorganic compounds and the formation of Secondary Organic Aerosol.     

Measurement of the carbonaceous component in the Milan urban particulate matter

The carbonaceous component in the Milan urban particulate matter, i.e. the two components black carbon (BC) and organic carbon (OC), has been measured by means of a thermogravimetric analyzer combined with an infrared spectrophotometer (TGA/FT-IR). While black carbon may be considered a primary pollutant, organic carbon includes both primary emissions and secondary organic aerosols. Since carbonaceous aerosol (including a small quantity of inorganic carbon, too) makes up roughly from 25% to 50% of the average annual PM 2.5 mass concentration, a deeper understanding of this component is required. The TGA/FT-IR technique, employed for the first time to our knowledge for the quantification of the particulate matter carbonaceous component, allows, thought the results here presented are preliminary, to assess the two components BC and OC in a simple way especially if compared with the methods reported in the literature. The total carbon (TC) determinations performed by TGA/FT-IR on Milan urban particulate matter are in good agreement with the results obtained by a total organic carbon (TOC) analyzer operating directly on the solid sample.     

Polycyclic aromatic hydrocarbons in the atmosphere: monitoring, sources, sinks and fate. II: Sinks and fate

This paper reviews the transformation processes that polycyclic aromatic hydrocarbons (PAHs) undergo in the atmosphere. These processes can take place both in the gas phase and in the particulate/aerosol one. Among the gas-phase processes, the most important ones are the daytime reaction with *OH and the nighttime reaction with *NO3. The relative importance of the two processes depends on the particular PAH molecule. For instance, gaseous naphthalene is mainly removed from the atmosphere upon reaction with *OH, while gaseous phenanthrene is mainly removed by reaction with *NO3. Oxy-, hydroxy-, and nitro-PAHs are the main transformation intermediates. Reaction with ozone and photolysis play a secondary role in the transformation of gaseous PAHs. The particle-associated processes are usually slower than the gas-phase ones, thus the gas-phase PAHs usually have shorter atmospheric lifetimes than those found on particulate. Due to the higher residence time on particulate when compared with the gas phase, direct or assisted photolysis plays a relevant role in the transformation of particle-associated PAHs. Among the other processes taking place in the condensed phase, nitration plays a very important role due to the health impact of nitro-PAHs, some of them being the most powerful mutagens found so far in atmospheric particulate extracts.     

Experimental study of a broad-band XeCl double-pass amplifier with SBS mirror

An oscillator-amplifier XeCl laser system has been used to experimentally investigate the effectiveness of a liquid stimulated Brillouin scattering (SBS) mirror for correcting the spatial aberrations of broad-band laser radiation in a double-pass amplifier. It has been found that the SBS amplifier performance is strongly dependent on the intensity I _p exciting the Brillouin medium. A good beam reconstruction has been attained at I _p1GW/cm², whereas highly aberrated output beams have been delivered by the SBS amplifier for I _p>1 GW/cm². By comparing the broad-band SBS amplifier performance to that of the same amplifier with a dielectrically coated flat mirror at one end, it has been found that the use of a SBS mirror is advantageous to obtain lower divergence output beams only for low energy pump beams (<1 mJ).     

The reaction Yb+O2 → YbO + O in a crossed molecular beam experiment

Dissociation energy (D_o = 4.29 ± 0.05 eV), threshold energy (E = 0.83 ± 0.05 eV) and forward scattering at a collision-al energy E_c = 1.1 cV have been found by crossing beam of Yb atoms with a supersonic seeded beam of He + O₂ at collisional energies up to E_c = 1.4 eV.