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Employing a cleavable carbohydrate–peptide linker, a new strategy for single-bead analysis of multivalent cyclic neoglycopeptides based on Edman degradation is described. Edman degradation of glycopeptides is hampered by the acid lability of the glycosidic bond and potential incompatibilities of phenylthiohydantoin (PTH) derivatives of glycosylated amino acids with PTH derivatives of the proteinogenic amino acids. To overcome this problem, carbohydrates are detached from the cyclopeptide templates before single-bead analysis, allowing for micro sequencing under routine conditions. With this strategy, application of multivalent cyclic neoglycopeptides in split-mix libraries with a subsequent screening process becomes possible for the first time.  相似文献   
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Starch belongs to the polyglucan group. This type of polysaccharide shows a broad β-relaxation process in dielectric spectra at low temperatures, which has its molecular origin in orientational motions of sugar rings via glucosidic linkages. This chain dynamic was investigated for α(1,4)-linked starch oligomers with well-defined chain lengths of 2, 3, 4, 6, and 7 anhydroglucose units (AGUs) and for α(1,4)-polyglucans with average degrees of polymerization of 5, 10, 56, 70, and so forth (up to 3000; calculated from the mean molecular weight). The activation energy (Ea) of the segmental chain motion was lowest for dimeric maltose (Ea = 49.4 ± 1.3 kJ/mol), and this was followed by passage through a maximum at a degree of polymerization of 6 (Ea = 60.8 ± 1.8 kJ/mol). Subsequently, Ea leveled off at a value of about 52 ± 1.5 kJ/mol for chains containing more than 100 repeating units. The results were compared with the values of cellulose-like oligomers and polymers bearing a β(1,4)-linkage. Interestingly, the shape of the Ea dependency on the chain length of the molecules was qualitatively the same for both systems, whereas quantitatively the starch-like substances generally showed higher Ea values. Additionally, and for comparison, three cyclodextrins were measured by dielectric relaxation spectroscopy. The ringlike molecules, with 6, 7, and 8 α(1,4)-linked AGUs, showed moderately different types of dielectric spectra. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 188–197, 2004  相似文献   
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In spherically symmetric systems, in spite of Birkhoff's Theorem, the rates of clocks in vacuum regions on either side of moving mass shells must be continually readjusted to stay in synchrony. This shows up as time-dependence of the metric in terms of the globally meaningful time coordinate.  相似文献   
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The magnetic structures of Mn1-xFexWO4 with x = 0.0, 0.16, 0.21, 0.225, 0.232, 0.24, 0.27, 0.29, and 1.0 were refined from neutron powder diffraction data. The magnetic phase diagram could be completed in the coexistence range of different magnetic structures up to x = 0.29. For the magnetic state at 1.5 K a commensurate antiferromagnetic structure with a propagation vector = (±1/4, 1/2, 1/2) was found for x ⩽ 0.22 while the magnetic spins order with = (1/2, 0, 0) for x ≥ 0.22. In the latter phase, additionally, weak magnetic reflections indexed to an incommensurate ordering with = (- 0.214, 1/2, 0.457) occur in the diffraction pattern up to x = 0.29 indicating the occurence of a reentrant phase. For 0.12 ⩽ x ⩽ 0.29 the low temperature phases are separated from a magnetic high temperature phase showing only magnetic reflections indexed to a spin arrangement with = (1/2, 0, 0). The magnetic phase diagram is discussed qualitatively considering random superexchange between the statistically distributed Mn2+- and Fe2+-ions in the coexistence range 0.12 ⩽ x ⩽ 0.29 of different magnetic structures related to those of pure MnWO4 and FeWO4. Received 9 October 2002 Published online 14 March 2003  相似文献   
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