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Barton esters have been introduced into the side chain of carbohydrates with high yields in only a few steps from easily available glycals. Their radical reactions afford 2-C-methyl and 2-C-bromomethyl hexoses, pentoses and disaccharides in good yields in analytically pure form. Since the Barton esters have been synthesized by an oxidative radical addition and their transformations by reductive radical processes, our results demonstrate the power of such reactions in carbohydrate chemistry.
Inorganic minerals form a major component of lacustrine sediments and have the potential to reveal detailed information on previous climatic and hydrological conditions. The ability to extract such information however, has been restricted by a limited understanding of the relationships between minerals and the environment. In an attempt to fill in this gap in our knowledge, 146 surface sediment samples have been investigated from 146 lakes on the Tibetan Plateau. The mineral compositions derived from these samples by X-Ray Diffraction (XRD) were used to examine the relationships between mineral compositions and the environmental variables determined for each site. Statistical techniques including Multivariate regression trees (MRT) and Redundancy Analysis (RDA), based on the mineral spectra and environmental variables, reveal that the electrical conductivity (EC) and Mg/Ca ratios of lake water are the most important controls on the composition of endogenic minerals. No endogenic minerals precipitate under hyper-fresh water conditions (EC lower than 0.13 mS/cm), with calcite commonly forming in water with EC values above 0.13 mS/cm. Between EC values of 0.13 and 26 mS/cm the mineral composition of lake sediments can be explained in terms of variations in the Mg/Ca ratio: calcite dominates at Mg/Ca ratios of less than 33, whereas aragonite commonly forms when the ratio is greater than 33. Where EC values are between 26 and 39 mS/cm, monohydrocalcite precipitates together with calcite and aragonite; above 39 mS/cm, gypsum and halite commonly form. Information on the local geological strata indicates that allogenic (detrital) mineral compositions are primarily influenced by the bedrock compositions within the catchment area. By applying these relationships to the late glacial and Holocene mineral record from Chaka Salt Lake, five lake stages have been identified and their associated EC conditions inferred. The lake evolved from a freshwater lake during the late glacial (before 11.4 cal. ka BP) represented by the lowest EC values (< 0.13 mS/cm), to a saline lake with EC values slightly higher than 39 mS/cm during the early and mid Holocene (ca. 11.4-5.3 cal. ka BP), and finally to a salt lake (after 5.3 cal. ka BP). These results illustrate the utility of our mineral-environmental model for the quantitative reconstruction of past environmental conditions from lake sediment records.
Applications based on Forster resonance energy transfer (FRET) play an important role for the determination of concentrations and distances within nanometer-scale systems in vitro and in vivo in many fields of biotechnology. Semiconductor nanocrystals (Quantum dots - QDs) possess ideal properties for their application as FRET acceptors when the donors have long excited state lifetimes and when direct excitation of QDs can be efficiently suppressed. Therefore, luminescent terbium complexes (LTCs) with excited state lifetimes of more than 2 ms are ideal FRET donor candidates for QD-acceptors. This chapter will give a short overview of theoretical and practical background of FRET, QDs and LTCs, and present some recent applications of LTC-QD FRET pairs for multiplexed ultra-sensitive in vitro diagnostics and nanometer-resolution molecular distance measurements.
Previous studies have revealed that infants aged 6-10 months are able to use the acoustic correlates of major prosodic boundaries, that is, pitch change, preboundary lengthening, and pause, for the segmentation of the continuous speech signal. Moreover, investigations with American-English- and Dutch-learning infants suggest that processing prosodic boundary markings involves a weighting of these cues. This weighting seems to develop with increasing exposure to the native language and to underlie crosslinguistic variation. In the following, we report the results of four experiments using the headturn preference procedure to explore the perception of prosodic boundary cues in German infants. We presented 8-month-old infants with a sequence of names in two different prosodic groupings, with or without boundary markers. Infants discriminated both sequences when the boundary was marked by all three cues (Experiment 1) and when it was marked by a pitch change and preboundary lengthening in combination (Experiment 2). The presence of a pitch change (Experiment 3) or preboundary lengthening (Experiment 4) as single cues did not lead to a successful discrimination. Our results indicate that pause is not a necessary cue for German infants. Pitch change and preboundary lengthening in combination, but not as single cues, are sufficient. Hence, by 8 months infants only rely on a convergence of boundary markers. Comparisons with adults' performance on the same stimulus materials suggest that the pattern observed with the 8-month-olds is already consistent with that of adults. We discuss our findings with respect to crosslinguistic variation and the development of a language-specific prosodic cue weighting.