Total synthesis of apoptolidin: completion of the synthesis and analogue synthesis and evaluation

The total synthesis of apoptolidin (1) is reported together with the design, synthesis, and biological evaluation of a number of analogues. The assembly of key fragments 6 and 7 to vinyl iodide 3 via dithiane coupling technology was supplemented by a second generation route to this advanced intermediate involving a Horner-Wadsworth-Emmons coupling of fragments 22 and 25. The final stages of the synthesis featured a Stille coupling between vinyl iodide 3 and vinylstannane 2, a Yamaguchi lactonization, a number of glycosidations, and final deprotection. The developed synthetic technology was applied to the construction of several analogues including 74, 75, and 77 which exhibit significant bioactivity against tumor cells.     

Vortex-assisted liquid-liquid microextraction of octylphenol, nonylphenol and bisphenol-A

A new and fast equilibrium-based solvent microextraction technique termed vortex-assisted liquid-liquid microextraction (VALLME) has been developed and used for the trace analysis of octylphenol, nonylphenol and bisphenol-A in water and wastewater samples. According to VALLME, dispersion of microvolumes of a low density extractant organic solvent into the aqueous sample is achieved by using for the first time vortex mixing, a mild emulsification procedure. The fine droplets formed could extract target analytes towards equilibrium faster because of the shorter diffusion distance and larger specific surface area. Upon centrifugation the floating extractant acceptor phase restored its initial single microdrop shape and was used for high-performance liquid chromatographic analysis. Different experimental parameters were controlled and the optimum conditions found were: 50 μl of octanol as the extractant phase; 20 ml aqueous donor samples; a 2 min vortex extraction time with the vortex agitator set at a 2500 rpm rotational speed; centrifugation for 2 min at 3500 rpm; no ionic strength or pH adjustment. The calculated calibration curves gave high levels of linearity yielding correlation coefficients (r²) greater than 0.9935. The repeatability and reproducibility of the proposed method were found to be good and the limits of the detection were calculated in the low μg l⁻¹ level ranging between 0.01 and 0.07 μg l⁻¹. Matrix effects were determined by applying the proposed method to spiked tap, river water and treated municipal wastewater samples. The proposed method was finally applied to the determination of target pollutants in real wastewater effluent samples using the standard addition method.     

Global Solutions to a Model for Exothermically Reacting,Compressible Flows with Large Discontinuous Initial Data

 We prove the global existence of solutions of the Navier-Stokes equations describing the dynamic combustion of a compressible, exothermically reacting fluid, and we study the large-time behavior of solutions, giving necessary and sufficient conditions for complete combustion in certain cases. The adiabatic constants and specific heats of the burned (product) and unburned (reactant) fluids may differ, and the initial data may be large and discontinuous. (Accepted August 31, 2002) Published online January 9, 2003 Communicated by C. M. Dafermos     

High-spin molecules: A mixed-valence Mn6 octahedron with an S = 11 ground state

The employment of 1,1,1-tris(hydroxymethyl)ethane ligand in higher oxidation state Mn cluster chemistry has yielded a new hexanuclear, mixed-valence (II,III,IV) compound with a rare [Mn₆(μ₆-O)]¹⁸⁺ octahedral core. The Mn₆ molecule is completely ferromagnetically coupled and possesses an S = 11 ground state, the maximum for a Mn^II, 2Mn^III, 3Mn^IV species.     

Far-red luminescent ruthenium pyridylimine complexes; building blocks for multinuclear arrays

Ruthenium(II) pyridylimine complexes are explored for their potential as units that might be incorporated into electronic or photonic arrays. The complexes [Ru(bipy)2(L)][PF6]2 (1) and [Ru(tpy)(L)Cl][BF4] (2) with L = phenylpyridin-2-ylmethylene-amine are synthesized and fully characterised using X-ray diffraction analysis and (2D) NMR spectroscopy. 1 displays emission in the far-red area of the spectrum at room temperature. The emission is significantly shifted to longer wavelength with respect to [Ru(bpy)3]2+ indicating that the lowest MLCT state is localised on the pyridylimine ligand. 2 is non-emissive at room temperature and at 77 K.     

Phytochemical analysis of young fustic (Cotinus coggygria heartwood) and identification of isolated colourants in historical textiles

Young fustic (Cotinus coggygria Scop.; Anacardiaceae) has been used as a dyestuff since antiquity. Phytochemical investigation of the methanol extract of the heartwood has led to the isolation and structure elucidation by nuclear magnetic resonance and mass spectrometry (MS) of 3′,4′,6-trihydroxyaurone (sulfuretin) and 3′,4′,7-trihydroxyflavonol (fisetin) as well as 3′,4′,7-trihydroxyflavanol (fustin), 3′,4′,5,7-tetrahydroxyflavonol (quercetin), 3′,4′,5,7-tetrahydroxyflavanol (taxifolin), 4′,7-dihydroxyflavanol, 3′,4′,7-trihydroxyflavanone (butin), 4′,7-dihydroxyflavanone (liquiritigenin), trans-2′,3,4,4′-tetrahydroxychalcone (butein), 4′,5,7-trihydroxyflavanone and trans-2′,4,4′-trihydroxychalcone (isoliquiritigenin). The isolated compounds were used as reference materials for the development of a high-performance liquid chromatography–diode array detector–MS method, which was then applied to analyse (1) fresh silk samples dyed with young fustic, (2) dyed silk subjected to artificially accelerated light ageing and (3) historical silk micro-samples, extracted from ecclesiastical post-Byzantine garments (fifteenth to eighteenth century), which belong to monasteries of Mount Athos. Sulfuretin and fisetin, which are usually used as markers for the identification of the yellow dye and, for the first time, some of the aforementioned flavonoid components of young fustic were identified in the historical extracts. Furthermore, preliminary experiments suggested that although the amounts of the dye components decrease with light ageing, the relative ratio of fisetin and sulfuretin, after a first step of ageing, seems to be almost unaffected by such degradation processes raised by light. The effect of the latter on the morphology of the dyed silk fibres is briefly investigated by scanning electron microscopy.     

Cytotoxic Evaluation and Determination of Organic and Inorganic Eluates from Restorative Materials

Over the last years, diverse commercial resin-based composites have dominated as dental filling materials. The purpose of the present study was to determine organic and inorganic eluates from five restorative materials using GC/MS and ICP–OES and to compare the effect on cell survival of human gingival fibroblasts of a conventional and a bioactive resin. Five commercially available restorative materials were employed for this study: Activa^TM Bioactive Restorative, ENA HRi, Enamel plus HRi Biofunction, Fuji II LC Capsule, and Fuji IX Capsule. Disks that were polymerized with a curing LED light or left to set were immersed in: 1 mL methanol or artificial saliva for GC/MS analysis, 5mL deionized water for ICP–OES, and 5mL of culture medium for cell viability. Cell viability was investigated with a modified staining sulforhodamine B assay.The following organic substances were detected: ACP, BHT, BPA, 1,4-BDDMA, CQ, DBP, DMABEE, HEMA, MCE, MeHQ, MOPA, MS, TMPTMA, and TPSb and the ions silicon, aluminum, calcium, sodium, and barium. Activa Bioactive Restorative was found to be biocompatible. Elution of organic substances depended on material’s composition, the nature of the solvent and the storage time. Ions’ release depended on material’s composition and storage time. The newly introduced bioactive restorative was found to be more biocompatible.     

Evaluation of chlorophyll fluorescence and membrane injury in the leaves of barley cultivars under osmotic stress

Two physiological tests for screening drought tolerance of barley (Hordeum vulgare, L.) plants are compared in this work. Water deficit is induced by treating the plants' roots with polyethylene glycol (PEG 8000). The relative water content (RWC) of the plants is used as a measure of the water status. Conductometrically determined electrolyte leakage from the leaf tissue demonstrates the membrane injury caused by dehydration. It is shown that the injury index increases with the decrease of the RWC of the leaves. The F(v)/F(m) ratio is employed to assess changes in the primary photochemical reactions of the photosynthetic apparatus after dehydration. The results suggest that PSII is weakly affected by the imposed osmotic stress. The fluorescence behaviour of the examined cultivars is related to their RWC.