On forced fast oscillations for delay differential equations on compact manifolds

We prove an existence result for forced oscillations of delay differential equations on compact manifolds with nonzero Euler-Poincaré characteristic. When the period is smaller than the delay we need the asymptotic fixed point index theory for C¹ maps due to Eells and Fournier, and Nussbaum.     

How important are temperature effects for cluster polarizabilities?

State-of-the-art first-principle all-electron density functional theory calculations on small sodium clusters are performed to study the temperature dependency of their polarizabilities. For this purpose Born-Oppenheimer molecular dynamics simulations with more than 100,000 time steps (>200 ps) are recorded employing gradient corrected functionals in combination with a double-zeta valence polarization basis set. For each cluster 18 trajectories between 50 and 900 K are collected. The cluster polarizabilities are then calculated along these trajectories employing a triple-zeta valence polarization basis set augmented with field-induced polarization functions. The analysis of these calculations shows that the temperature dependency of the sodium cluster polarizabilities varies strongly with cluster size. For several clusters characteristic changes in the polarizability per atom as a function of temperature are observed. It is shown that the inclusion of finite temperature effects resolves the long-standing mismatch between calculated and measured sodium cluster polarizabilities.     

Electrostatic interactions between a protein and oppositely charged micelles

Micellar solutions made of a fully fluorinated surfactant, LiPFN, form water-soluble complexes with lysozyme in a wide concentration range. Such complexes are stabilized by electrostatic and, very presumably, double-layer interactions. The mixtures were investigated by combining electrophoretic mobility, DLS, and dielectric relaxation methods. The former gives information on the surface charge density of protein-micelle complexes and indicates that the resulting adducts retain a negative charge (i.e., charge neutralization is incomplete). The double-layer thickness of proteins, micelles, and protein-micelle complexes is also connected to the dielectric relaxation frequency. Changes in particle size (inferred by DLS), charge density, and double-layer thickness are closely interrelated to each other. A model was developed to quantify such properties.     

Synthesis and Ruthenium-Catalyzed Enantioselective Hydrogenation of 3-O-Substituted 1,3-Dihydroxypropan-2-ones. Part 2

A number of 3-O-substituted 1,3-dihydroxypropan-2-ones have been synthesized in view of their potential use as prochiral precursors of optically active glycerols. Indeed, the oxo-ethers have been reduced to the corresponding 3-O-substituted glycerols via chiral Ru complexes derived from (S)-binap, ( =(?)-(S)-2,2′-bis(diphenylphosphino)-1,1′-binaphthalene) with enantiomeric excesses up to 93%. The steric course of the catalytic reduction appears to be essentially dependent on the steric encumbrance of the substituents; indeed, a dramatic increase of the enantiomeric excess is observed when the bulky trityl group is substituted by the less encumbering benzyl or octadecyl groups.     

Asymmetric synthesis and structure-activity studies of the fungal metabolites colletorin A,colletochlorin A and their halogenates analogues

The first asymmetric total synthesis of both enantiomers of the natural products colletorin A and colletochlorin A is presented. The proposed methodology is based on the coupling reaction between highly substituted aromatic Gilman cuprates and optically active allyl bromides, in turn obtained by Sharpless asymmetric dihydroxylation. The latter ensured a high degree of regio- and stereocontrol in the enantioselective step of the synthesis. The same synthetic strategy has been also applied for the preparation of differently halogenated synthetic analogues of colletochlorin A in high enantiomeric purity. The enantioselective synthesis of colletorin A and colletochlorin A allows to reliably assign their absolute configuration. Preliminary assessment of their herbicidal and insecticidal properties evidence the possibility to modulate the bioactivity of these compounds, highlighting its dependence on both the absolute stereochemistry and the halogen nature.     

Organic contamination in clams,Venerupis aurea laeta and Cerastoderma edule glaucum,from Sicily (Italy)

Two species of edible clams Venerupis aurea laeta and Cerastoderma edule glaucum from Ganzirri Lake (Sicily, Italy) were investigated to determine OCP and PCB residues by GC-MS. Thirty-five samples were examined for two years in order to perform: a) their actual contamination; b) the daily dietary exposure of seafood consumers to the pollutants in question. In all the clams analysed in this study, PCB and OCP (4,4′-DDE) residues are always below the limits fixed by law. It seems that there is some seasonality of concentrations observed. In fact the more high concentrations of residues are detected in the hot months, for both species and years. Given the consumption of clams and the values obtained in this study for the two species analysed, it is possible estimate that the average daily dietary intake of NDL-PCB and of 4,4′-DDE for adults is really low.     

Thermodynamic temperature differences from the ITS-90 for the correction of thermodynamic property data

This paper purpose is to re-calculate thermodynamic or chemical–physical properties according to thermodynamic temperature T, where measured temperature values were obtained according to the ITS-90, T₉₀ (or the reverse). The main aims of the calculations are: to remove the discontinuity of the first derivative at 273.16 K that is intrinsic in the ITS-90 definition; to use a single cubic spline to model the database of the available experimental data over the whole temperature range (2.37 to 1235) K, while maximising the medium-range smoothness of the correction function; to compute corrections using only local polynomial coefficients.     

Lipase-catalyzed preparation of corticosteroid 17α-esters endowed with antiandrogenic activity

Several 17α-monoesters of cortexolone and its Δ⁹-derivative are endowed with antiandrogenic activity. Their synthesis can be accomplished by means of a lipase-catalyzed chemoselective alcoholysis of the corresponding 17α,21-diesters.     

Gas-liquid phase separation in oppositely charged colloids: stability and interfacial tension

We study the phase behavior and the interfacial tension of the screened Coulomb (Yukawa) restricted primitive model (YRPM) of oppositely charged hard spheres with diameter sigma using Monte Carlo simulations. We determine the gas-liquid and gas-solid phase transitions using free energy calculations and grand-canonical Monte Carlo simulations for varying inverse Debye screening length kappa. We find that the gas-liquid phase separation is stable for kappasigma相似文献   

Structure and stereochemistry of a new cytotoxic polychlorinated sulfolipid from Adriatic shellfish

A detailed analysis of the causative toxins contained in the hepatopancreas of toxic mussels from the northern Adriatic sea has been carried out. Along with some DSP (diarrhetic shellfish poisoning) type toxins, such as okadaic acid, yessotoxin, and their derivatives, which are involved in a number of human intoxications throughout the world, we have now isolated a new cytotoxin, a polychlorinated sulfolipid 1, whose gross structure has been elucidated by spectral analysis, including various 2D NMR techniques. The relative stereochemistry of 1 was elucidated by successful application of the J-based configuration analysis developed for acyclic compounds using carbon-proton spin-coupling constants ((2,3)J(C,H)) and proton-proton spin-coupling constants ((3)J(H,H)); its absolute stereochemistry was established by the Mosher method. Compound 1 possesses in vitro cytotoxicity against WEHI 164 and RAW 264.7 cells.