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.     

Long-Term Changes in a Heat Exchanger Steel

The steel ASTM A213 P22 is used for superheater outlet header in power plants. During duty cycles lasting over tens of years the temperature is of the order of 545°C and the pressure 125 atm. The microscopic changes in these steels are hard to analyze under working conditions, but they are believed to be responsible for the appearance of creeps in such devices. Investigation of the microscopic modifications will help to predict future failures due to creeps, increasing the reliability and saving a lot of money.We report the investigation of such changes in ASTM A213 P22 steel in use for 30 years as a Superheater header at Haifa power station. The analysis has been carried out using Mössbauer Spectroscopy, X-ray diffraction and optical microscopy. As a result it seems that the morphology and phase change of the carbide phases M₃C/M₇C₃ and M₂₃C₆ are the most prominent changes leading to the material failures.     

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.     

The stereocontrolled synthesis of orthogonally protected (R)-α-methyltryptophan

An expedient and highly stereocontrolled route to (R)-α-methyltryptophan and its orthogonally protected analogs has been developed via a four-step conversion from L-alanine in good overall yields. The stereochemistry of the products is confirmed by X-ray diffraction analysis, NMR spectroscopy and optical rotations.     

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.     

Effects of variable selection on CoMFA coefficient contour maps in a set of triazines inhibiting DHFR

Summary An example of a CoMFA study is described with the aim to discuss one of the major problems of this 3D QSAR method: lack of variable selection. It is shown that the use of nonrelevant energy parameters might produce CoMFA contour maps which poorly reflect the actual nature of the binding site and are in part statistical artefacts. The data set employed in our analysis comparises triazine inhibitors of dihydrofolate reductase (DHFR), isolated from chicken liver, which have already been the object of a QSAR study by other authors. Since three-dimensional structures of triazine-DHFR complexes are known, it was possible not only to reduce ambiguities in the superimposition of the ligands, but also to compare the resulting CoMFA contour maps with the enzyme active site.Supplementary material available: The Cartesian coordinates and the atomic charges of the PM3-optimized structures used in the CoMFA study are available as MOL2 files upon request.To whose memory this paper is dedicated.     

RESOLUTION OF THE INDIVIDUAL TRYPTOPHANYL CONTRIBUTIONS TO THE NEAR-ULTRAVIOLET DICHROIC ACTIVITY OF APOMYOGLOBIN

Abstract –The individual tryptophanyl contributions to the near-ultraviolet dichroic activity of apomyoglobin in its native conformation have been resolved. This was accomplished by comparing the spectra of two classes of apomyoglobin with different aromatic residue contents and observing the effect of a specific modification of indole residues. The circular dichroism (CD) spectra of apomyoglobins containing two tryptophanyl residues, i.e. Trp A-5 and A-12, show the presence of a positive peak centered at 292 nm, attributable to indolic chromophore, which is missing in the CD spectrum of tuna apomyoglobin possessing only Trp A-12. Moreover, the specific modification of Trp A-5 by 2-hydroxy-5-nitrobenzyl bromide is shown by the lack of the 292 nm peak and the appearance of a positive band at longer wavelength. The pH dependence of the position of this band suggests that it arises from the 2-hydroxy-5-nitrobenzyl moiety. The results suggest that Trp A-12 does not substantially contribute to the optical activity in the near ultraviolet.