Stereospecific uncatalyzed alpha-O-glycosylation and alpha-C-glycosidation by means of a new D-Gulal-derived alpha vinyl oxirane

The reaction of alpha vinyl oxirane 5, prepared through a new route to the d-gulal system, with O-nucleophiles (alcohols and di-O-isopropylidene-alpha-d-monosaccharides) and C-nucleophiles (lithium alkyls) affords, in a completely stereoselective way, the corresponding 2-unsaturated alpha O- and C-glycosides having the same configuration as the starting epoxide.     

Probing the glycosidic linkage: UV and IR ion-dip spectroscopy of a lactoside

The beta(1-->4) glycosidic linkage found in lactose is a prevalent structural motif in many carbohydrates and glycoconjugates. Using UV and IR ion-dip spectroscopies to probe benzyl lactoside isolated in the gas phase, we find that the disaccharide unit adopts only a single, rigid structure. Its fully resolved infrared ion-dip spectrum is in excellent agreement with that of the global minimum structure computed ab initio. This has glycosidic torsion angles of phi(H) (H1-C1-O-C4') approximately 180 degrees and psi(H) (C1-O-C4'-H4') approximately 0 degrees which correspond to a rotation of approximately 150 degrees about the glycosidic bond compared to the accepted solution-phase conformation. We discuss the biological implications of this discovery and the generality of the strategies employed in making it.     

Engineering protein therapeutics: predictive performances of a structure-based virtual affinity maturation protocol

The implementation of a structure based virtual affinity maturation protocol and evaluation of its predictivity are presented. The in silico protocol is based on conformational sampling of the interface residues (using the Dead End Elimination/A* algorithm), followed by the estimation of the change of free energy of binding due to a point mutation, applying MM/PBSA calculations. Several implementations of the protocol have been evaluated for 173 mutations in 7 different protein complexes for which experimental data were available: the use of the Boltzamnn averaged predictor based on the free energy of binding (ΔΔG(*)) combined with the one based on its polar component only (ΔΔE(pol*)) led to the proposal of a subset of mutations out of which 45% would have successfully enhanced the binding. When focusing on those mutations that are less likely to be introduced by natural in vivo maturation methods (99 mutations with at least two base changes in the codon), the success rate is increased to 63%. In another evaluation, focusing on 56 alanine scanning mutations, the in silico protocol was able to detect 89% of the hot-spots.     

Enantioselective reduction and deracemisation using the non-conventional yeast Pichia glucozyma in water/organic solvent biphasic systems: preparation of (S)-1,2-diaryl-2-hydroxyethanones (benzoins)

Water/organic solvent two-liquid-phase systems have been successfully applied in the synthesis of enantiomerically pure (S)-benzoin through two different methodologies catalysed by whole cells from the non-conventional yeast Pichia glucozyma: the stereoselective monoreduction of benzil and the deracemisation of benzoin. The presence of the organic solvent influences the redox systems implied in the reactions, avoiding the formation of the corresponding diols, increasing the enantioselectivity and allowing the easy isolation of the products in high yields and excellent enantiomeric excesses. The use of both strategies has been extended to the preparation of different chiral benzoin derivatives.     

Production of octadienal in the marine diatom Skeletonema costatum

[reaction: see text] Marine diatoms produce alpha,beta,gamma,delta-unsaturated aldehydes that have detrimental effects on the reproduction of their natural predators. The production of these defensive metabolites is suggested to involve enzymatic oxidation of polyunsaturated fatty acids. In this paper, feeding experiments with labeled precursor provide clear evidence in support of the origin of octadienals 1 and 2 from 6,9,12-hexadecatrienoic acid (5), thus proving the involvement of novel lipoxygenase/lyase activity for the oxidation of C(16) fatty acids.     

Inclusion complexes of rosmarinic acid and cyclodextrins: stoichiometry,association constants,and antioxidant potential

The interaction between β-cyclodextrin (β-CD) and the polyphenol rosmarinic acid (RA) is here reported by ¹H NMR titration experiments. The formation of an aqueous soluble inclusion complex is confirmed and valuable information regarding mode of penetration of guest into β-CD, stoichiometry, and stability of the complex is obtained. The analysis by the continuous variation method shows the undoubted formation of 1:1 β-CD/RA complex. Additionally, the estimated apparent association constants reveal the importance of the asymmetry of the RA in the complexation; the incorporation of the catechol moiety closer to the carboxylic group is more favorable (K?=?2,028 M^?1) than from the other end of the RA molecule (K?=?1,184 M^?1). Finally, we have also investigated the antioxidant activity and storage stability of the β-CD/RA complexed system; the presence of β-CD was found to produce a remarkable enhancement on the antioxidant activity.     

Sustainable Three‐Component Synthesis of Isothioureas from Isocyanides,Thiosulfonates, and Amines

Multiple applications of isothioureas as fine chemicals (or their precursors) are known, but a general sustainable method for their synthesis was hitherto unavailable. We report a novel general approach towards S‐alkyl and S‐aryl isothioureas through a copper(I)‐catalyzed three‐component reaction between amines, isocyanides, and thiosulfonates. The formal synthesis of a superpotent sweetener further illustrates the applicability of our method.     

A Hemi‐metallocene Chromium Catalyst with Trimethylaluminum‐Free Methylaluminoxane for the Synthesis of Disentangled Ultra‐High Molecular Weight Polyethylene

Recently, it has been shown that by using a single‐site catalytic system having titanium as a metallic center, it is possible to tailor the entanglement density in the amorphous region of a semi‐crystalline ultra‐high molecular weight polyethylene (UHMWPE). This route provides the possibility to make high‐modulus, high‐strength uniaxially and biaxially drawn tapes and films, without using any solvent during processing. In this publication, it is shown that a single‐site catalyst having chromium as metallic center, proposed by Enders and co‐workers, can also be tuned to provide control on the entanglement density during synthesis of the UHMWPE. However, to achieve the goal some modifications during the synthesis are required. The synthesized polymers can be processed in the solid state below the equilibrium melting temperature, resulting in uniaxially drawn tapes having tensile strength and modulus greater than 3.5 N/tex and 200 N/tex, respectively. Rheological studies have been performed to follow the increase in entanglement density in melt state with time.