Thermotropic liquid crystalline glycolipids

Are the liquid crystalline properties of the materials of living systems important in biological structures, functions, diseases and treatments? There is a growing consciousness that the observed lyotropic, and often thermotropic liquid crystallinity, of many biological materials that possess key biological functionality might be more than curious coincidence. Rather, as the survival of living systems depends on the flexibility and reformability of structures, it seems more likely that it is the combination of softness and structure of the liquid-crystalline state that determines the functionality of biological materials. The richest sources of liquid crystals derived from living systems are found in cell membranes, of these glycolipids are a particularly important class of components. In this critical review, we will examine the relationship between chemical structure and the self-assembling and self-organising properties of glycolipids that ultimately lead to mesophase formation.     

Iodoacetoxylation Reaction: A Convenient Route to α-Glycosides in the 2-Iodo and 2-Deoxy Series

Abstract

Iodoacetoxylation of 3,4,6-tri-O-acetyl-1,5-anhydro-2-deoxy-D-arabino-hex-1-enitol (tri-O-acetyl-D-glucal) (1) and 3,4-di-O-acetyl-1,5-anhydro-2,6-dideoxy-L-arabino-hex-1-enitol (di-O-acetyl-L-rhamnal) (3) gave the α-1,2-trans-1-O-acetyl-2-deoxy-2-iodo adducts with high stereoselectivities and good yields, in accordance with the results reported on 3,6-di-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-1,5-an-hydro-2-deoxy-D-arabino-hex-1-enitol (hexa-O-acetyl lactal) (2). The α-1,2-trans adducts were reacted with an excess of alcohol in the presence of trimethylsilyl trifluoromethane-sulfonate affording the corresponding α-1,2-trans-2-deoxy-2-iodo-glycopyranosides in good yields. The octyl 2-deoxy-2-iodo-α-D-glycosides 10 and 11 prepared in two steps from the glycals 1 and 2 were deiodinated and deacetylated, giving 28 and 29, and the physicochemical-properties (cmc) of 29 are reported.     

Introducing Mutations to Modify the C13/C9 Ratio in Linoleic Acid Oxygenations Catalyzed by Rabbit 15‐Lipoxygenase: A QM/MM and MD Study

Lipoxygenases (LOs) are a family of nonheme iron‐containing enzymes that catalyze the hydroperoxidation of several polyunsaturated fatty acids with a huge regio‐ and stereospecificity. Mammalian 15‐LO‐1 yields almost exclusively oxygenation at the C13 position of the linoleic acid (LA), its preferred substrate. This is very important because metabolites derived from oxidation in distinct positions produce opposite physiological effects. We have combined here quantum mechanics/molecular mechanics calculations with molecular dynamics simulations to show how a suitable mutation of the rabbit 15‐LO‐1 enzyme can produce a significant amount of products derived from oxygenation at the C9 position of LA. In effect, the Leu597Val or Leu597Ala mutants are predicted to lead to a diminution of the oxygenation C13/C9 ratio in LA as huge as five orders of magnitude. This shows that the conserved residue Leu597 actually drives the regiospecific hydroperoxidation of LA catalyzed by 15‐LO‐1 enzyme.     

Is Regioselectivity in the Enzyme‐Catalyzed Hydroperoxidation of Arachidonic Acid Necessarily Determined by Hydrogen Abstraction? The Case of Rabbit Leu597Ala/Ile663Ala ALOX15 Mutant

Molecular dynamics simulations and quantum mechanics/molecular mechanics calculations were performed on the in silico Leu597Ala/Ile663Ala double mutant of rabbit ALOX15 (12/15 lipoxygenase). The computational results suggested that subtle steric hindrance by the conserved Leu597 and C‐terminal Ile663 residues disturbed H10 abstractions in wildtype ALOX15 (which abstracts H13), but if these two bulky residues were mutated to smaller ones, H10 abstraction was no longer impeded and the regioselectivity of the initial H‐abstraction step was changed. However, site‐directed mutagenesis with HPLC analysis of the products of the whole oxidation process showed that the regioselectivity of the hydroperoxidation was not altered. This disagreement may be explained by the conformational reorganization of the system needed to rotate the ?OO^. group from an antarafacial to a suprafacial arrangement prior to back‐hydrogen transfer. After H10 abstraction and O₂ insertion, the evolution of the peroxy radical at C12 was sterically impeded, whereas peroxyl group rotation at C15 (after H13 abstraction) could easily evolve to a suprafacial arrangement, which thus led to the final product. For this reason, the global regiospecificity was not affected in the mutant. These findings exemplify that the regioselectivity of initial hydrogen abstraction and the regioselectivity of the final product do not necessarily coincide (in fact, they can be opposite) for the hydroperoxidation of arachidonic acid catalyzed by a lipoxygenase.     

A folk model structure on omega-cat

The primary aim of this work is an intrinsic homotopy theory of strict ω-categories. We establish a model structure on ωCat, the category of strict ω-categories. The constructions leading to the model structure in question are expressed entirely within the scope of ωCat, building on a set of generating cofibrations and a class of weak equivalences as basic items. All objects are fibrant while free objects are cofibrant. We further exhibit model structures of this type on n-categories for arbitrary n∈N, as specializations of the ω-categorical one along right adjoints. In particular, known cases for n=1 and n=2 nicely fit into the scheme.     

A note on the characteristic classes of non-positively curved manifolds

In this expository note, we give a simple conceptual proof of the Hirzebruch proportionality principle for Pontrjagin numbers of non-positively curved locally symmetric spaces. We also establish (non)-vanishing results for Stiefel–Whitney and Pontrjagin numbers of (finite covers of) the Gromov–Thurston examples of compact negatively curved manifolds. A byproduct of our argument gives a constructive proof of a well-known result of Rohlin: every closed orientable 3-manifold bounds orientably. We mention some geometric corollaries: a lower bound for degrees of covers having tangential maps to the non-negatively curved duals and estimates for the complexity of some representations of certain uniform lattices.     

Synthesis of magnetic noble metal (nano)particles

Noble metal particles can be made strongly ferromagnetic or diamagnetic provided that they are synthesized in a sufficiently strong magnetic field. Here we outline two synthesis methods that are fast, reproducible, and allow broad control over particle sizes ranging from nanometers to millimeters. From magnetometry and light spectroscopy, it appears that the cause of this anomalous magnetism is the surface anisotropy in the noble metal particles induced by the applied magnetic field. This work offers an elegant alternative to composite materials of noble metals and magnetic impurities.     

Algebra and Geometry of Rewriting

We present various results of the last 20 years converging towards a homotopical theory of computation. This new theory is based on two crucial notions: polygraphs (introduced by Albert Burroni) and polygraphic resolutions (introduced by François Métayer). There are two motivations for such a theory:

• Providing invariants of computational systems to study those systems and prove properties about them;
• Finding new methods to make computations in algebraic structures coming from geometry or topology.

This means that this theory should be relevant for mathematicians as well as for theoretical computer scientists, since both may find useful tools or concepts for their own domain coming from the other one.