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Selected AbstractsSynthesis, NMR, and Conformational Studies of Cyclic Oligo-(1,6)-,- D -Glucosamines,EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 13 2010Marina L. Gening Abstract The first synthesis of a series of homologous cyclic oligo-(1,6)-,- D -glucosamines consisting of two to seven residues and representing a new type of functionalized cyclic oligosaccharides is reported. Remarkably high yields of the studied macrocyclization reaction irrespective of the length of the acyclic precursors were observed. In the case of compounds constituted of four to seven glucosamine units ,-stereoisomers formed as side products despite the presence of a strongly participating 2- N -phthaloyl group to control ,-glycosylation. Both phenomena may be accounted for by conformational features of the linear bifunctional precursors. According to computer modeling and NMR conformational studies, the described linear (1,6)-,-linked oligoglucosamines exist in a right-handed helix-like conformation, in which the glycosyl donor and acceptor moieties are prearranged in a way that facilitates intramolecular glycosylation from the ,-side. Prepared cyclo-oligoglucosamines differ in their conformational flexibilities, as illustrated by their spectral characteristics and calculated asphericity distributions. Moreover, the obtained compounds do not possess a distinct hydrophobic cavity, which is in contrast to the well-known cyclodextrins. All these characteristics provide an excellent basis for the use of these novel cyclic oligosaccharides as scaffolds for the construction of biomolecular conjugates. [source] Modular Microreaction Systems for Homogeneously and Heterogeneously Catalyzed Chemical SynthesisHELVETICA CHIMICA ACTA, Issue 1 2005Daniel Until now, microreaction devices designed for a specific type of reaction were used mainly for highly exothermic, very fast reactions. Described is a modular microreaction system and its application to representative homogeneous and heterogeneous reactions important in organic synthesis. The modular microreaction system allows continuous flow processes to be optimized and employed effectively in the chemical laboratory. The modular microreaction systems proved also versatile for syntheses requiring moderate reaction times, thus extending their application to a large fraction of organic reactions. The use of the modular and cleanable microreaction systems to rapidly develop optimized reaction conditions provides an excellent basis for the development of many chemical transformations scalable from milligram to ton production quantities. [source] Trends in savanna structure and composition along an aridity gradient in the KalahariJOURNAL OF VEGETATION SCIENCE, Issue 3 2002R.J. Scholes Abstract. The Kalahari sand sheet occupies 2.5 million ha in southern Africa. It is an area with relatively similar deep aeolian soils, and a strong south to north gradient in rainfall, from 200 to 1000 mm mean annual precipitation (MAP) in the region studied. This provides an excellent basis for gradient studies at the subcontinental scale. This paper briefly reviews the literature on the vegetation of the Kalahari and describes the vegetation structure and composition at 11 new sites. There is a clear gradient in woody plant biomass (as indexed by basal area) from south to north. Above the minimum level of 200 mm MAP, the woody basal area increases at a rate of ca. 2.5 m2.ha -1 per 100 mm MAP. Mean maximum tree height also increases along the gradient, reaching 20 m at ca. 800 mm MAP. The number of species to contribute > 95% of the woody basal area increases from one at 200 mm to 16 at 1000 mm MAP. Members of the Mimosaceae (mainly Acacia) dominate the tree layer up to 400 mm MAP. They are replaced by either the Combretaceae (Combretum or Terminalia) or Colophospermum mopane of the Caesalpinaceae between 400 and 600 mm MAP, and by other representatives of the Caesalpinaceae above 600 mm MAP. The vegetation is largely deciduous up to 1000 mm MAP, except for species that apparently have access to groundwater, which may be locally dominant above about 600 mm MAP. [source] A new sample of broad absorption-line quasars exhibiting the ghost of Lyman ,MONTHLY NOTICES OF THE ROYAL ASTRONOMICAL SOCIETY, Issue 4 2006Matthew North ABSTRACT We have searched the broad absorption-line quasar (BAL QSO) sample presented recently by Reichard et al. for objects exhibiting the so-called ,ghost of Lyman ,'. This ghost manifests as a hump near ,5900 km s,1 in the troughs of the broad absorption lines and provides strong evidence for the importance of line driving in powering the outflows from BAL QSOs. Of the 224 sample BAL QSOs selected from the Sloan Digital Sky Survey Early Data Release, 198 satisfy our redshift constraints and 58 show clear evidence of multiple-trough (MT) structure in the C iv 1550 Å line. A composite spectrum constructed from this MT sample already shows evidence for a ghost feature. Narrowing our classification scheme further, we define a set of 36 objects that individually show evidence of a ghost feature, and then apply further cuts to arrive at a final ,best sample' that contains our seven strongest ghost candidates. A further five objects show evidence for a ghost feature that is almost strong enough to merit inclusion in our best sample. Despite its limited size, our best sample more than doubles the number of known BAL QSOs with clear ghost signatures and should make an excellent basis for detailed follow-up studies. [source] Chemical characterization of Azadirachta indica grafted on Melia azedarach and analyses of azadirachtin by HPLC-MS-MS (SRM) and meliatoxins by MALDI-MSPHYTOCHEMICAL ANALYSIS, Issue 4 2010Moacir Rossi Forim Abstract Introduction , Melia azedarach adapted to cool climates was selected as rootstocks for vegetative propagation of Azadirachta indica. Cleft grafting of A. indica on M. azedarach rootstock showed excellent survival. Little is known about the chemistry of grafting. Objective , The roots, stems, leaves and seeds of this graft were examined in order to verify if grafted A. indica would produce limonoids different from those found in non-grafted plants. Intact matured fruits were also studied to verify if they were free of meliatoxins. Methodology , After successive chromatographic separations the extracts afforded several limonoids. HPLC-MS/MS and MALDI-MS were used to develop sensitive methods for detecting azadirachtin on all aerial parts of this graft and meliatoxins in fruits, respectively. Results , The stem afforded the limonoid salannin, which was previously found in the oil seeds of A. indica. Salannin is also found in the root bark of M. azedarach. Thus, the finding of salannin in this study suggests that it could have been translocated from the M. azedarach rootstock to the A. indica graft. HPLC-MS/MS analyses showed that azadirachtin was present in all parts of the fruits, stem, flowers and root, but absent in the leaves. The results of MALDI-MS analyses confirmed the absence of meliatoxins in graft fruits. Conclusion , This study showed that A. indica grafted onto M. azedarach rootstock produces azadirachtin, and also that its fruits are free of meliatoxins from rootstocks, confirming that this graft forms an excellent basis for breeding vigorous Neem trees in cooler regions. Copyright © 2010 John Wiley & Sons, Ltd. [source] | ||||||||||