A weight-function approach for determining watershed initial conditions for combustion waves

In many generic combustion models, one finds that a combustionwave will develop with a specific wave speed. However, thereare possible initial temperature profiles which do not evolveinto such waves, but rather die out to the ambient temperature.There can exist, in some models, a clear distinction betweenthose initial conditions that do evolve into combustion wavesand those that do not; this is sometimes referred to as thewatershed initial condition. When fuel consumption is consideredto be negligible, analytical methods can be used to obtain theexact watershed. In this paper, we consider the problem of determiningpseudo-watersheds and ascertaining the relationship betweenthese pseudo-watersheds and the exact watersheds. In the processa novel weight-function approach for infinite spatial domainsis developed.     

Synthesis of cytotoxic cyanobactin,Wewakazole B

We report herein the synthesis of cytotoxic cyanobactin, Wewakazole B through an efficient solution-phase approach. The key steps of the synthesis are the macrocyclic lactamization of linear dodecapeptide and construction of two hexapeptides with three different substituted oxazole rings.     

Determination of the formation constant for the inclusion complex of methyl-β-cyclodextrin with anticoagulant durgs warfarin and 8-chlorowarfarin in aqueous solution

Inclusion of anticoagulant drugs within the cavity of methyl--cyclodextrin in aqueous solution was studied by ultraviolet absorption, fluorimetry and reversed-phase liquid chromatography. Formation constants were obtained for complex formation of methyl--cyclodextrin with warfarin and 8-chlorowarfarin.     

Aromatization of 3,4-dihydro-β-carboline-3-qarboxylic acid and its derivatives through a carbanion intermediate : mechanistic study and use in chemical synthesis

3,4-dlhydro-β-carboline-3-carboxylic acid , its esters and amide derivatives (AH₂) undergo complete aromatization into corresponding β-carboline derivatives (A) by basic treatment under mild conditions. This, together with the easy obtention of 3,4-dihydro-β-carboline from the parent N^αformyltryptophan derivatives constitutes an attractive possibility to obtain complex molecules containing the β-carboline ring. The mechanism of the reaction was investigated by polarography, U.V.spectrometry and polarimetry. In alcaline media, (AH₂) undergoes two successive equilibria : the first yielding a C₃ carbanion occurs with suppression of the chirality while the second yields a thermodynamically preferred C₄ carbanion which undergoes aromatization through an oxidative pathway (K'_a = 2×10^-14 at 45°C).     

New markers to identify the provenance of lapis lazuli: trace elements in pyrite by means of micro-PIXE

Lapis lazuli has been used for glyptics and carving since the fifth millennium BC to produce jewels, amulets, seals, inlays, etc; the identification of the origin of the stone used for carving artworks may be valuable for reconstructing old trade routes. Since ancient lapis lazuli art objects are precious, only non-destructive techniques can be used to identify their provenance, and ion beam analysis (IBA) techniques allow us to characterise this stone in a fully non-invasive way. In addition, by using an ion microprobe, we have been able to focus the analysis on single crystals, as their typical dimensions may range from a few microns to hundreds of microns. Provenance markers, identified in previous IBA studies and already presented elsewhere, were based on the presence/absence of mineral phases, on the presence/quantity of trace elements inside a phase and on characteristic features of the luminescence spectra. In this work, a systematic study on pyrite crystals, a common accessory mineral in lapis lazuli, was carried out, following a multi-technique approach: optical microscopy and SEM-EDX to select crystals for successive trace element micro-PIXE measurements at two Italian facilities, the INFN Laboratori Nazionali di Legnaro and the INFN LABEC laboratory in Firenze. The results of this work allowed us to obtain new markers for lapis lazuli provenance identification.     

Mechanism of two-electron oxidation of deoxyguanosine 5'-monophosphate by a platinum(IV) complex

Many transition metal complexes mediate DNA oxidation in the presence of oxidizing radiation, photosensitizers, or oxidants. The final DNA oxidation products vary depending on the nature of metal complexes and the structure of DNA. Here we propose a mechanism of oxidation of a nucleotide, deoxyguanosine 5'-monophosphate (dGMP) by trans-d,l-1,2-diaminocyclohexanetetrachloroplatinum (trans-Pt(d,l)(1,2-(NH(2))(2)C(6)H(10))Cl(4), [Pt(IV)Cl(4)(dach)]; dach = diaminocyclohexane) to produce 7,8-dihydro-8-oxo-2'-deoxyguanosine 5'-monophosphate (8-oxo-dGMP) stoichiometrically. The reaction was studied by high-performance liquid chromatography (HPLC), (1)H and (31)P nuclear magnetic resonance (NMR), and electrospray ionization mass spectrometry (ESI-MS). The proposed mechanism involves Pt(IV) binding to N7 of dGMP followed by cyclization via nucleophilic attack of a phosphate oxygen at C8 of dGMP. The next step is an inner-sphere, two-electron transfer to produce a cyclic phosphodiester intermediate, 8-hydroxyguanosine cyclic 5',8-(hydrogen phosphate). This intermediate slowly converts to 8-oxo-dGMP by reacting with solvent H(2)O.