Cardiac glycosides: 5. Stereoselective syntheses of digitoxigenin α-D, β-D, α-L,and β-L-glucosides

As part of a continuing study of cardiac g1ycos1des,^1,2 stereoselective syntheses of the four possible glucosides of digitoxigenin were developed via the thermodynamically produced tetra-O-benzyl-D- and L-glucosyl α-trichloroacetaimidates 2α and 11α, and the kinetically produced β-trichloroacetaimidates 2β and 11β. A 58%:19% isolated yield ratio of α-D and β-D benzyl protected glycosides 6 and 3 could be obtained in 30 minutes reaction at ?10°. Halide ion catalysis with a 2:1 excess of tetra-O-benzyl-α-D-glucopyranosyl bromide for 14 days in methylene chloride at room temperature gave a 39%:11% ratio of 6 and 3, along with 43% of recovered digitoxigenin. Debenzylation of the D-glucosides required milder conditions (20% Pd/C, atmospheric pressure, 45 min-1 hr) than the L-glucosides (40% Pd/C, 2 hr) but yields were typically 80% for both groups.     

Scattering of light by deformed disordered spherulites

The change in the light-scattering patterns upon deforming two-dimensional disordered spherulites is shown to arise from four effects occurring upon stretching: (1) the change in shape of the spherulite, (2) the change in average orientation of the optic axes of the scattering volume elements, (3) the change in deviation of the optic axis orientation angle from its average value, and (4) the change in the distance over which this deviation is correlated. The effects of these contributions upon the experimental scattering patterns are analyzed.     

A novel type secoiridoid glucoside,hydrangenoside a from Hydrangea macrophylla

Hydrangenoside A, isolated along with its three congeners from Hydrangea macrophylla, was proved to have a novel type of structure which is thought to be biosynthesized through an aldol-type condensation of secologanin with a unit formed by the shikimate-malonate route followed by decarboxylation.     

Thermally stimulated current from extended-chain crystals of polyethylene

Thermally stimulated current (TSC) has been observed in extended-chain crystals of polyethylene above room temperature. The TSC spectra exhibit two current peaks of opposite polarity. The peaks were separated into separate components by curve fitting. The position of the negative peak, which appears at 123°C, is independent of charging conditions. The positive current increases after γ irradiation or aging of the samples.     

Photochemical vapor deposition of amorphous silicon through 185 nm excitation of monosilane

Photochemical vapor deposition of a-Si films at a high rate using SiH₄ and a 185 nm low pressure mercury lamp is described. A maximum rate of 1 nm/sec was attained using the 185 nm lamp. This rate was about ten times higher than that using a 254 nm lamp. Assuming that there is no interaction between the effects of the two wavelengths, the deposition rate per light output power of 184.9 nm light is 160 times larger than that for 253.7 nm light. The absorption cross-section of the 184.9 nm light is ten times greater than that for the 253.7 nm light.     

Signalling crosstalk in FGF2-mediated protection of endothelial cells from HIV-gp120

Background  

The blood brain barrier (BBB) is the first line of defence of the central nervous system (CNS) against circulating pathogens, such as HIV. The cytotoxic HIV protein, gp120, damages endothelial cells of the BBB, thereby compromising its integrity, which may lead to migration of HIV-infected cells into the brain. Fibroblast growth factor 2 (FGF2), produced primarily by astrocytes, promotes endothelial cell fitness and angiogenesis. We hypothesized that treatment of human umbilical vein endothelial cells (HUVEC) with FGF2 would protect the cells from gp120-mediated toxicity via endothelial cell survival signalling.