Hydrophobized laminarans as new biocompatible anti-oomycete compounds for grapevine protection.

Laminaran, a ß-(1→3)-glucan extracted from Laminaria digitata, is a known elicitor of plant defenses, but provides only low level of disease control in vineyard trials. In this context, laminaran was partly hydrophobized by grafting from 1.6 to 7.6 lauryl chains to the native saccharidic chain and the impact of sulfation of the hydrophobized glucans was studied. The activity of the different synthetized laminaran derivatives as antimicrobial agents against Plasmopara viticola, the causal agent of grape downy mildew, and as elicitors of defense reactions in planta, was evaluated. Our results showed that acylation imparts an antimicrobial activity to laminaran which is related to the degree of acylation, AL3, with 7.6 lauryl chains, being the most effective derivative. Sulfation of the acylated laminarans did not further increase the antimicrobial activity. Our results also demonstrated that the efficacy of AL3 against Plasmopara viticola was most likely due to the direct antimicrobial activity of the lauryl chains rather than to an elicitation of plant defenses.

In vitro kinetic study of growth and mineralization of osteoblast-like cells (Saos-2) on titanium surface coated with a RGD functionalized bisphosphonate.

Osteoconduction and osseointegration are the critical stages for implantation success. Peptides containing RGD (Arg-Gly-Asp) adhesive sequence are known to promote cell adhesion and consequently to favor osseointegration of medical devices. In this study, RGD peptides were coupled to a bisphosphonate used as an anchor system and chemically adsorbed on polished titanium discs. Two different concentrations, 10(-10) mol/L (RGD 10(-10)) and 10(-4) mol/L (RGD 10(-4)) were compared to non coated discs (RGD 0). Adhesion, spreading, and mineralization of osteoblast-like cells (Saos-2) were assessed. Mineralization kinetic was done at 3, 6, 10, 14, and 18 days of culture; the extent of mineral deposits was quantified by image analysis. Histogram repartitions of nuclear area, characterizing cell spreading, showed a shift to higher values in cells cultured on RGD coated titanium disks. Mineralization started at day 3 in the three groups, but had a faster development in the RGD 10(-10) group from day 6 to day 18 compared to RGD 0 and RGD 10(-4). At day 18, the percentage of mineralized area was significantly higher for RGD 10(-10) compared to RGD 0 (p < 0.05). In the present study, this new method was found suitable to anchor RGD containing species on titanium: this favored adhesion and spreading of osteoblast-like cells and mineralization compared to noncoated titanium.

Tuning selectivity in macrotricyclic carbohydrate receptors; CH-->N mutations in aromatic spacers.

Dipicolinoyl spacer groups are used to control the conformational and H-bonding properties of tricyclic carbohydrate receptors 3 and 4. Binding selectivities are changed in relation to all-isophthaloyl system 1b.

Phase transfer of monosaccharides through noncovalent interactions: selective extraction of glucose by a lipophilic cage receptor.

We have previously shown that macrotricyclic host 1a is a powerful receptor for glucopyranosyl units in the nonpolar medium of chloroform. However, the solubility properties of 1a did not permit studies of the extraction of carbohydrates from aqueous solution. This paper describes the synthesis of the new variant 1b, furnished with a highly lipophilic exterior array of 12 benzyloxy substituents. In homogeneous solution, 1b behaves much as 1a, binding n-octyl beta-d-glucoside with K(a) = 720 M(-1) in CD(3)OH/CDCl(3) (8:92). In two-phase experiments, the improved solubility of 1b allows carbohydrate extraction to be observed. Three hexoses (glucose, galactose, and mannose), two pentoses (ribose and xylose), and the two methyl glucosides are all extracted substantially into chloroform from 1 M aqueous solutions. Among the hexoses, 1b shows notable affinity and selectivity for glucose, extracting detectable amounts even from 0.1 M aqueous solutions.

Supramolecular self-assembling properties of membrane-spanning archaeal tetraether glycolipid analogues.

The self-assembling properties of a new series of archaeal tetraether glycolipid analogues 1-6 that are characterized by a bipolar architecture with two similar or different glycosidic and/or phosphate polar heads and a lipid core possessing a cyclopentane unit and/or branched chains were studied by means of differential scanning calorimetry, optical microscopy, X-ray scattering, freeze-fracture electron microscopy and dynamic light scattering. Unsymmetrical phosphate derivatives 1 and 2 spontaneously formed thermostable multilamellar and unilamellar vesicles in which most of the bipolar lipids adopted a trans-membrane conformation, as revealed by freeze-fracture electron microscopy. Supramolecular aggregates of neutral glycolipids 3-6 were found to depend on both the saccharidic polar heads and the chain composition. The presence of one glycosidic residue with rather marked hydrophilic properties, such as the lactosyl moiety, was required to allow the formation of multilamellar vesicles. Surprisingly, the introduction of a cyclopentane unit in the bridging chain was able to induce an apparent two-by-two membrane association: this unusual behaviour might be the result of unsymmetrical interfacial properties of the lipid layer caused by the presence of the cyclopentane unit.

Synthetic Approaches to Novel Archaeal Tetraether Glycolipid Analogues.

Symmetrical and unsymmetrical archaeal tetraether glycolipid analogues have been prepared. The syntheses are based upon the elaboration of lipid cores from versatile chiral starting materials followed by simultaneous or sequential introduction of polar headgroups. Three pathways (A-C) were elaborated for the synthesis of stereochemically defined lipids 14-16 characterized by a straight bridging spacer and two dihydrocitronellyl chains attached to glycerol units at the sn-3 and sn-2 positions, respectively. Pathway C appeared to be particularly advantageous for the synthesis of tetraether 9, which possesses a cyclopentane unit as found in thermoacidophilic lipids. Diglycosylated lipids 4-6 were produced in 49-53% yields by reaction of diols 14-16 with beta-D-galactofuranosyl donor 31, whereas unsymmetrical lipids possessing either two different carbohydrate units 7 or a saccharidic moiety and a phosphate group 8 were efficiently prepared from monoprotected diol 35. These compounds represent the first examples of tetraether-type analogues containing a phosphate unit and/or glycosyl moieties.