Chiral spiro Cu(I) complexes. Supramolecular stereocontrol and isomerisation dynamics by the use of TRISPHAT anions

Association of enantiopure TRISPHAT anion (1) with chiral spiro [Cu(LL')2] complexes (LL' = 2-R-phen, 2, 6-R-bpy, 3, and 2-iminopyridine, 4) leads to an efficient NMR enantiodifferentiation. Variable temperature 1H NMR spectroscopy has been used to determine the isomerisation kinetics of these pseudo-tetrahedral complexes and to evaluate their configurational stability; the latter depending on the structure of the diimine ligands. In the case of the 2-anthracenyl-phen derivative, a decent level of supramolecular stereocontrol was noted (d.e. up to 45%); the configuration of the complex being determined by electronic circular dichroism (ECD).     

Optimization of pressurized liquid extraction of Piper gaudichaudianum Kunth leaves

Piperaceae family is original from tropical regions and it shows more than 700 species around the world. Piper gaudichaudianum Kunth is the specie more abundant in Brazil, occurring from Northeast to South Brazil. In this paper, it was investigated the influence of some experimental parameters on the pressurized liquid extraction (PLE) of P. gaudichaudianum Kunth leaves, using petroleum ether as extractor solvent. The optimization of the main variables involved in the PLE process (extraction temperature and time) has been done by response surface methodology (RSM) using, as responses, the extraction yield and the chromatographic profile (GC/MS) of the extracts. The optimized procedure employed 3 g of ground leaves, 10 min of extraction and one cycle of extraction at 85 degrees C. The major compounds present in the petroleum ether extracts were: palmitic acid, stearic acid and nerolidol. The results presented in this work show the possibility of using a fast and easy process to recover compounds from P. gaudichaudianum Kunth.     

Features of the low-temperature specific heat in underdoped YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>6 + <Emphasis Type="Italic">x</Emphasis></Subscript> single crystals

The behavior of the low-temperature specific heat C(T) for YBa₂Cu₃O_{6 + x} single crystals with the doping level corresponding to the normal phase has been studied by the relaxation technique at different values of the applied magnetic field. It has been found that the C(T)/T plot exhibits such an anomaly as a steep increase with decreasing temperature from T about 4 K down to T ≤ 2 K (the minimum temperature value accessible in the experiment). The applied magnetic field as high as 9 T inverts this anomaly and leads to a sharp drop in C(T)/T during cooling within the same temperature range. A model involving the Schottky-type centers formulated in this work and the data on spin correlation functions has allowed us to calculate the temperature dependence of the specific heat, which fits the experimental curves quite well.     

Spinning Strings,Black Holes and Stable Closed Timelike Geodesics

The existence and stability under linear perturbation of closed timelike curves in the spacetime associated to Schwarzschild black hole pierced by a spinning string are studied. Due to the superposition of the black hole, we find that the spinning string spacetime is deformed in such a way to allow the existence of closed timelike geodesics.     

Effect of strong intersite correlations on the mixing of band and localized states of the periodic Anderson model

It has been shown in the limit of the low density of band carriers that the inclusion of the strong intersite interaction between electrons within the framework of the periodic Anderson model results in two qualitatively new features in its energy structure. The first feature is associated with the appearance of an additional quasi-localized level, which significantly changes the structure of the electronic density of states. The second feature is the strong renormalization of the effective constant of hybridization with the bare localized level.     

YC‐1, an activation inductor of soluble guanylyl cyclase

The crystal structure of 1‐benzyl‐3‐(5‐hydroxy­methyl‐2‐furyl)­indazole, C₁₉H₁₆N₂O₂, showed that the furan O and indazole N atoms lie on the same face of the mol­ecule. The crystal packing consists of intermolecular hydrogen bonding, and indazole–indazole and indazole–phenyl interactions.     

Synthesis and characterization of functionalized core-shell γFe2O3-SiO2 nanoparticles

Amino and/or polyethyleneglycol (PEG) functionalized core-shell γFe₂O₃-SiO₂ magnetic nanoparticles were synthesized and characterized. Amino-PEG-functionalized core-shell nanoparticles have calibrated sizes and a good colloidal stability. These bi-functionalized core-shell nanoparticles are potentially useful as biocompatible particles for magnetically targeted chemotherapy.     

Fluctuations in bounded cells of liquid crystals in an external field

Spatial correlation functions of orientation fluctuations in bounded cells of smectic and nematic liquid crystals are calculated taking into account the effect of external fields and finiteness of the energy of anchoring to the surface. The cases of positive and negative anisotropies of magnetic susceptibility or permittivity are considered. The calculations are based on the division of degrees of freedom into bulk and surface ones and on the reduction of the computation of the continual integral determining the correlation function to the solution of the Euler equation with corresponding boundary conditions of the first or third kind. The obtained correlation functions are used for describing the intensity of light scattered in nematics for the planar and homeotropic orientations. It is shown, in particular, that the measurements of the angular dependence of the scattered light intensity may serve as a reliable method for determining the energy of anchoring of a liquid crystal to a substrate for different values of the external field.     

Full stereochemical understanding in a new (2R,3R,4R)-4-hydroxyisoleucine synthesis

We present the crystal and molecular structures of 2,3,6,7,8,8a-hexa­hydro-6,8-methano-7,7,8a-tri­methyl-3-(1-methyl-2-oxo­propyl­idene)-5H-1,4-benzoxazin-2-one, C₁₆H₂₁NO₃, (III), and 2,3,6,7,8,8a-hexa­hydro-3-(2-hydroxy-1-methyl­propyl)-6,8-methano-7,7,8a-tri­methyl-5H-1,4-benzoxazin-2-one, C₁₆H₂₅NO₃, (V). These compounds are two of the four key intermediates in our synthetic route to (2R,3R,4R)-4-hydroxy­isoleucine. The two structures provide a full understanding of the stereochemistry in successive steps. This synthesis was based on a new optically pure chiral oxazinone auxiliary derived from (1R,2R,5R)-2-hydroxy­pinan-3-one.     

Synthesis of polybutadiene‐based particles via dispersion ring‐opening metathesis polymerization

Latex particles based on 1,4‐polybutadiene were synthesized via dispersion ring‐opening metathesis copolymerization of 1,5‐cyclooctadiene with a α‐norbornenyl poly(ethylene oxide) macromonomer. Stable but polydisperse colloidal dispersions in the 50 nm to 10 μm size range were obtained. In this work, particular attention was paid to the effects of the kinetics of copolymerization on the structure of the graft copolymers formed and on the onset of turbidity. Strategies to prepare monodisperse polybutadiene particles were also designed through the growth of a polybutadiene shell from a well‐defined polynorbornene seed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1154–1163, 2004