Anomeric configuration-directed diastereoselective C-C bond formation in vinyl sulfone-modified carbohydrates: a general route to branched-chain sugars

[structure: see text] This is the first report on the diastereoselective addition of carbon nucleophiles to vinyl sulfone-modified hex-2-enopyranosides and pent-2-enofuranosides. Nucleophiles add to the C-2 position from a direction opposite to that of the disposition of the anomeric methoxy group. This novel concept of anomeric configuration-directed stereocontrolled carbon-carbon bond formation in vinyl sulfone-modified carbohydrates is general in nature and has been implemented in the synthesis of new hexopyranosyl and pentofuranosyl branched-chain sugars and densely functionalized carbohydrates.     

Phototoxicity in human lens epithelial cells promoted by St. John's Wort

St. John's Wort (SJW), an over-the-counter antidepressant, contains hypericin, which absorbs light in the UV and visible ranges and is phototoxic to skin. To determine if it also could be phototoxic to the eye, we exposed human lens epithelial cells to 0.1-10 microM hypericin and irradiated them with 4 J/cm2 UV-A or 0.9 J/cm2 visible light. Neither hypericin exposure alone nor light exposure alone reduced cell viability. In contrast, cells exposed to hypericin in combination with UV-A or visible light underwent necrosis and apoptosis. The ocular antioxidants lutein and N-acetyl cysteine did not prevent damage. Thus, ingested SJW is potentially phototoxic to the eye and could contribute to early cataractogenesis. Precautions should be taken to protect the eye from intense sunlight while taking SJW.     

Thermal decomposition of rare-earth trioxalatocobaltates

The thermal decomposition of rare-earth trioxalatocobaltates LnCo(C₂O₄)₃ · x H₂O, where Ln  La, Pr, Nd, has been studied in flowing atmospheres of air/oxygen, argon/ nitrogen, carbon dioxide and a vacuum. The compounds decompose through three major steps, viz. dehydration, decomposition of the oxalate to an intermediate carbonate, which further decomposes to yield rare-earth cobaltite as the final product. The formation of the final product is influenced by the surrounding gas atmosphere. Studies on the thermal decomposition of photodecomposed lanthanum trioxalatocobaltate and a mechanical mixture of lanthanum oxalate and cobalt oxalate in 1 : 2 molar ratio reveal that the decomposition behaviour of the two samples is different. The drawbacks of the decomposition scheme proposed earlier have been pointed out, and logical schemes based on results obtained by TG, DTA, DTG, supplemented by various physico-chemical techniques such as gas and chemical analyses, IR and mass spectroscopy, surface area and magnetic susceptibility measurements and X-ray powder diffraction methods, have been proposed for the decomposition in air of rare-earth trioxalatocobaltates as well as for the photoreduced lanthanum salt and a mechanical mixture of lanthanum and cobalt oxalates.     

A compton profile study of tantalum

We report the results of Compton profile study on polycrystalline tantalum. Measurements have been made using 59.54 keV gamma-rays. The results are compared with the APW band structure calculations of Papanicolaouet al and other available data. In contrast to the work of Changet al the overall agreement is better with the APW band structure which worsens on incorporating the electron correlation correction. Estimates of the errors due to the contribution from bremsstrahlung, non-validity of impulse-approximation and anomalous dispersion are also briefly discussed.     

Weakly nonlinear stability analysis of a falling film with countercurrent gas flow

Weakly nonlinear stability analysis of a falling film with countercurrent gas–liquid flow has been investigated. A normal mode approach and the method of multiple scales are employed to carry out the linear and nonlinear stability solutions for the film flow system. The results show that both supercritical stability and subcritical instability are possible for a film flow system when the gas flows in the countercurrent direction. The stability characteristics of the film flow system are strongly influenced by the effects of interfacial shear stress when the gas flows in the countercurrent direction. The effect of countercurrent gas flow in a falling film is to stabilize the film flow system.     

On the Poincare formula and the Riemann singularity theorem over nodal curves

The symmetric powers of a smooth curve determine effective cycles in the Jacobian of the curve. The classical Poincare formula expresses these cycles in terms of the powers of the theta divisor of the Jacobian. Here we prove an analogue of this well-known Poincare formula for the desingularisation of the compactified Jacobian of an irreducible nodal curve with arbitrary number of nodes. We also prove an analogue of the Riemann singularity theorem and show that these effective cycles are normal.     

Multifunctional antigens of A. fumigatus and specific antibodies

The majority of Aspergillus-induced infections in man are caused by the pathogenic fungus A. fumigatus, which secretes biologically and immunologically active glycosylated and nonglycosylated proteins. The complexity in the antigenic structure of A. fumigatus and the varying host immune responses lead to a wide spectrum of clinical conditions such as allergic bronchopulmonary aspergillosis (ABPA), aspergilloma, and invasive aspergillosis. It is reported that 15-20% of allergic asthmatics suffer from Aspergillus-induced allergies. The incidence of opportunistic infections, including Aspergillus infections, has risen because of the increase in the incidence of HIV and tuberculosis. Allergic bronchopulmonary aspergillosis is an immunologically significant clinical form where type I and type III hypersensitivity reactions are involved in pathogenesis. High levels of specific IgE and IgG antibodies in these patients are of diagnostic value. Molecular characterization of certain immunodominant allergens and antigens of A. fumigatus revealed the presence of complex carbohydrate moieties, heat-shock proteins, enzyme activities such as elastase, protease, catalase, dismutase, and cytotoxic ribonuclease. A Con A binding allergen/antigen (45 kDa) and Con A nonbinding allergen/antigen (18 kDa, Asp fI) have a multifunctional nature. The multifunctional nature of these antigens may play an important role in the pathogenesis of the disease. Significant amounts of a major allergen/antigen of molecular weight 18 kDa is excreted in large amounts through the urine of patients with invasive aspergillosis. Studies on the structure-function relationship of the 18-kDa allergen/antigen revealed the involvement of tryptophan residues in binding with monoclonal antibodies (MAbs). Also, the histidine residues and cysteine disulfide bonds of the 18-kDa allergen are involved in its catalytic activity. The high load of multifunctional antigens in the serum of patients for prolonged periods, the presence of high levels of specific antibodies, and the absence of protective antibodies in ABPA patients have necessitated studies on the functional properties of the antibodies. The present study shows significant immunoreactivity of antibodies in patients of ABPA to fibronectin and collagen. Analysis of IgG antibodies from the patients of ABPA showed the presence of DNA-cleaving activity. These observations offer a new line of thinking in understanding the mechanism of pathogenesis of Aspergillus-induced clinical manifestations, and may lead to novel approaches to intervention in the inflammation and infection caused by fungal pathogens.     

Temperature dependence of the lattice parameters in the S1G and S2G phases of HxBPA

The temperature dependence of the monoclinic lattice constants in the two smectic phases, S¹_G and S²_G, of HxBPA, has been obtained from X-ray diffraction data, in the temperature range 300 K < T < 240 K. The variation of b (unique axis) is consistent with the chain ordering in the S²_G phase indicated by Raman and NMR measurements.     

Highly diastereoselective oxidations of a thioether appended with a neighboring hydroxyl group

Highly diastereoselective oxidations of $\text{endo}$-alcohol $\text{1}$ to the corresponding sulfoxides, the relative stereochemistries of these sulfoxides and that of an intermediary alkoxysulfonium salt determined by X-ray crystallographic analysis is reported.