Versatile ruthenium(II) complexes allow for siteselective C À H oxygenations with weakly-coordinating aldehydes. The challenging C À H functionalizations proceed with high chemoselectivity by rate-determining C À H metalation. The new method features an ample substrate scope, which sets the stage for the step-economical preparation of various bioactive heterocycles.
The two lectins LecA from Pseudomonas aeruginosa and the B-subunit of Shiga toxin from Shigella dysenteriae (StxB) share the glycosphingolipid globotriaosylceramide (Gb3) as receptor. Counterintuitively, we found that LecA and StxB segregated into different domains after recognizing Gb3 at the plasma membrane of cells. We hypothesized that the orientation of the carbohydrate head group of Gb3 embedded in the lipid bilayer differentially influences LecA and StxB binding. To test this hypothesis, we reconstituted lectin-Gb3 interaction using giant unilamellar vesicles and were indeed able to rebuild LecA and StxB segregation. Both, the Gb3 fatty acyl chain structure and the local membrane environment, modulated Gb3 recognition by LecA and StxB. Specifically, StxB preferred more ordered membranes compared to LecA. Based on our findings, we propose comparing staining patterns of LecA and StxB as an alternative method to assess membrane order in cells. To verify this approach, we re-established that the apical plasma membrane of epithelial cells is more ordered than the basolateral plasma membrane. Additionally, we found that StxB recognized Gb3 at the primary cilium and the periciliary membrane, whereas LecA only bound periciliary Gb3. This suggests that the ciliary membrane is of higher order than the surrounding periciliary membrane.
The receptor lipid Gb3 is responsible for the specific internalization of Shiga toxin (STx) into cells. The head group of Gb3 defines the specificity of STx binding, and the backbone with different fatty acids is expected to influence its localization within membranes impacting membrane organization and protein internalization. To investigate this influence, a set of Gb3 glycosphingolipids labeled with a BODIPY fluorophore attached to the head group was synthesized. C24 fatty acids, saturated, unsaturated, α‐hydroxylated derivatives, and a combination thereof, were attached to the sphingosine backbone. The synthetic Gb3 glycosphingolipids were reconstituted into coexisting liquid‐ordered (lo)/liquid‐disordered (ld) giant unilamellar vesicles (GUVs), and STx binding was verified by fluorescence microscopy. Gb3 with the C24:0 fatty acid partitioned mostly in the lo phase, while the unsaturated C24:1 fatty acid distributes more into the ld phase. The α‐hydroxylation does not influence its partitioning.
In this work, the influence of the rigid substrate on the determination of the sample Young's modulus, the so‐called bottom‐effect artifact, is demonstrated by an atomic force microscopy force‐spectroscopy experiment. The nanomechanical properties of a one‐component supported lipid membrane (SLM) exhibiting areas of two different thicknesses are studied: While a standard contact mechanics model (Sneddon) provides two different elastic moduli for these two morphologies, it is shown that Garcia's bottom‐effect artifact correction yields a unique value, as expected for an intrinsic material property. Remarkably, it is demonstrated that the ratio between the contact radius (and not only the indentation) and the sample thickness is the key parameter addressing the relevance of the bottom‐effect artifact. The experimental results are validated by finite element method simulations providing a solid support to Garcia's theory. The amphiphilic nature of the investigated material is representative of several kinds of lipids, suggesting that the results have far reaching implications for determining the correct Young's modulus of SLMs. The generality of Garcia's bottom‐effect artifact correction allows its application to every kind of supported soft film.
Versatile ruthenium(II) complexes allow for site‐selective CH oxygenations with weakly‐coordinating aldehydes. The challenging CH functionalizations proceed with high chemoselectivity by rate‐determining CH metalation. The new method features an ample substrate scope, which sets the stage for the step‐economical preparation of various bioactive heterocycles.
The receptor lipid Gb 3 is responsible for the specific internalization of Shiga toxin (STx) into cells.The head group of Gb 3 defines the specificity of STx binding,and the backbone with different fatty acids is expected to influence its localization within membranes impacting membrane organization and protein internalization. To investigate this influence,aset of Gb 3 glycosphingolipids labeled with aB ODIPY fluorophore attached to the head group was synthesized. C 24 fatty acids, saturated, unsaturated, a-hydroxylated derivatives,and acombination thereof,w ere attached to the sphingosine backbone. The synthetic Gb 3 glycosphingolipids were reconstituted into coexisting liquid-ordered (l o )/liquid-disordered (l d )g iant unilamellar vesicles (GUVs), and STx binding was verified by fluorescence microscopy. Gb 3 with the C 24:0 fatty acid partitioned mostly in the l o phase,w hile the unsaturated C 24:1 fatty acid distributes more into the l d phase.T he a-hydroxylation does not influence its partitioning.
A mannosyl donor bearing a spiroannulated cyclopropane unit at C-5 has been prepared, and its behavior in glycosylation reactions investigated. Selectivities in favor of the β-anomer were observed. Corresponding di- and trisaccharides incorporating the rigid cyclopropane motif were assembled.
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