Die gleichzeitige Bestimmung von Methylalkohol und Formaldehyd in sehr kleinen Mengen in ein und derselben L?sung

Ohne Zusammenfassung     

Untersuchung von Seifen

Ohne Zusammenfassung     

Les dimensions d'un ensemble abstrait

Sans résumé     

Unusual reactivity of bicyclo[2.2.1]heptene derivatives during the ozonolysis. Part 2

The ozonation of four bornene derivatives, prepared from (R)-(+)-pulegone, which possess a particularly hindered double bond, led to the formation of unexpected products depending on the nature of the solvent. The formation of the corresponding epoxides, ketones with the same skeleton, various lactones and even an allyl alcohol and an allyl chloride (allylic functionalisation) was observed. In two cases, products presenting a pulegone modified skeleton resulting from a Wagner-Meerwein rearrangement were obtained. The structure of three products was confirmed by crystallographic X-ray analysis. Mechanisms taking into account the rigid and congested structure of the reactants explain these results. The most striking steps were backed up by theoretical calculations.     

Context-dependent effects of asparagine glycosylation on Pin WW folding kinetics and thermodynamics

Asparagine glycosylation is one of the most common and important post-translational modifications of proteins in eukaryotic cells. N-glycosylation occurs when a triantennary glycan precursor is transferred en bloc to a nascent polypeptide (harboring the N-X-T/S sequon) as the peptide is cotranslationally translocated into the endoplasmic reticulum (ER). In addition to facilitating binding interactions with components of the ER proteostasis network, N-glycans can also have intrinsic effects on protein folding by directly altering the folding energy landscape. Previous work from our laboratories (Hanson et al. Proc. Natl. Acad. Sci. U.S.A. 2009, 109, 3131-3136; Shental-Bechor, D.; Levy, Y. Proc. Natl. Acad. Sci. U.S.A. 2008, 105, 8256-8261) suggested that the three sugar residues closest to the protein are sufficient for accelerating protein folding and stabilizing the resulting structure in vitro; even a monosaccharide can have a dramatic effect. The highly conserved nature of these three proximal sugars in N-glycans led us to speculate that introducing an N-glycosylation site into a protein that is not normally glycosylated would stabilize the protein and increase its folding rate in a manner that does not depend on the presence of specific stabilizing protein-saccharide interactions. Here, we test this hypothesis experimentally and computationally by incorporating an N-linked GlcNAc residue at various positions within the Pin WW domain, a small β-sheet-rich protein. The results show that an increased folding rate and enhanced thermodynamic stability are not general, context-independent consequences of N-glycosylation. Comparison between computational predictions and experimental observations suggests that generic glycan-based excluded volume effects are responsible for the destabilizing effect of glycosylation at highly structured positions. However, this reasoning does not adequately explain the observed destabilizing effect of glycosylation within flexible loops. Our data are consistent with the hypothesis that specific, evolved protein-glycan contacts must also play an important role in mediating the beneficial energetic effects on protein folding that glycosylation can confer.     

A concise and convergent synthesis of PA-824

An efficient four-step synthesis of PA-824, a promising antituberculosis drug candidate, has been developed. This concise approach offers significant improvements over the synthetic route currently used for large-scale production.     

Near-field measurement of amplitude and phase in silicon waveguides with liquid cladding

Heterodyne near-field scanning optical microscopy (H-NSOM) has proven useful as a tool for characterization of both amplitude and phase of on-chip photonic devices in air, but it has previously been unable to characterize devices with a dielectric overcladding, which is commonly used in practice for such devices. Here we demonstrate H-NSOM of a silicon waveguide with a liquid cladding emulating the solid dielectric. This technique allows characterization of practical devices with realistic refractive index profiles. Fourier analysis is used to estimate the effective refractive index of the mode from the measured data, showing an index shift of 0.08 from air to water cladding, which is seen to correspond well to simulations.     

中微子的螺旋度反转

庆祝著名物理学家Maurice Goldhaber百岁生日的文章,该文的作者是Maurice Goldhaber本人(前美国布鲁克海文国家实验室主任)和他的儿子Alfred Scharff Goldhaber(美国纽约大学石溪分校杨振宁理论物理研究所教授).在文章中,Goldhaber父子阐明了粒子的螺旋度和手征性