RESUMEN

Fungi constitute an abundant source of natural polysaccharides, some of them harboring original structures which can induce responses in mammalian or plant cells. An alkaline extract from the edible mushroom Pleurotus ostreatus has been obtained and called Pleuran complex cell wall extract (CCWE). It consists of a glucan-peptide complex whose components fall in a quite broad range of molecular weights, from 30 to 80 kDa. Pleuran extract has been tested on cultivated plants in laboratory conditions and also during field trial for its capacity to stimulate plant defenses in response to pathogen attack. Following Pleuran CCWE treatment, enhanced levels of various biochemical markers associated with plant responses have been observed, including enzymatic activities (e.g., peroxidase) or expression of some pathogenesis-related genes. In addition, during field experiments, we have noticed significant reductions in disease symptom levels in relation to different plant/pathogen systems (wheat/septoria, vine/mildew). These results confirmed that Pleuran CCWE could be used as an elicitor of plant defenses and could help in reducing pesticide applications against plant pathogens.

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The Treignac water is a natural mineral water containing mainly orthosilicic acid. On inert substrates, it forms a silica film with fractal structures which cannot be reproduced in laboratory-reconstituted water. These structures form by condensation of orthosilicic acid monomers, following the Witten-Sander model of diffusion-limited aggregation. On biological surfaces, such as tomato leaves, the Treignac water forms a silica film with a different morphology and devoid of fractal structures. The filmogenic properties of this natural mineral water are here discussed in the context of crop protection, as the silica film can provide a barrier and a platform for the immobilization of elicitors of plant defense responses.

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Heavy silyl enol ethers (mostly TIPS and TBS) combine with cyclic N-alkenyl N-acyliminium salts generated in situ from their N,O-acetal precursors, to furnish highly functionalized indolizidines through an unprecedented double Mukaiyama-Mannich-Prins cascade transformation. This novel cascade annulation process demonstrates a promising scope, and takes place mostly catalytically with interesting stereocontrol. Furthermore, an appealing facet of this chemistry is emphasized with a bicatalytic approach by which the Mannich-Prins cascade follows a Ru-catalyzed N-allylamide to N-(E)-propenyl isomerization of the aminal counterpart in a one-pot operation.

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Xylans were purified from delignified holocellulose alkaline extracts of Castanea sativa (Spanish chestnut) and Argania spinosa (Argan tree) and their structures analyzed by means of GC of their per-trimethylsilylated methylglycoside derivatives and (1)H NMR spectroscopy. The structures deduced were characteristic of a 4-O-methylglucuronoxylan (MGX) and a homoxylan (HX), respectively, with degrees of polymerization ranging from 182 to 360. In the case of MGX, the regular or random distribution of 4-O-methylglucuronic acid along the xylosyl backbone--determined by MALDI mass spectrometry after autohydrolysis of the polysaccharide--varied and depended both on the botanical source from which they were extracted and on the xylan extraction procedure. The MGX also inhibited in different ways the proliferation as well as the migration and invasion capability of A431 human epidermoid carcinoma cells. These biological properties could be correlated with structural features including values of the degree of polymerization, 4-O-MeGlcA to xylose ratios, and distribution of 4-O-MeGlcA along the xylosyl backbone, giving evidence of a defined structure-activity relationship.

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A glucuronoxylan was purified from a delignified holocellulose alkaline extract of Castanea sativa (Spanish chestnut) and its structure analyzed by means of FT-IR, GC of the per-trimethylsilylated methylglycoside derivatives, and 1H and 13C NMR spectroscopy. The results supported a structure based on a linear polymer of xylopyranose units linked with beta(1-->4) bonds in which, on average, one out of every six units is substituted at C-2 by a 4-O-methylglucuronic acid unit; this structure is typical of a hardwood acidic 4-O-methylglucuronoxylan (MGX) with an estimated degree of polymerization of 200. The MGX from C. sativa inhibited the proliferation of A431 human epidermoid carcinoma cells with an IC50 value of 50 microM. In addition, this xylan inhibited A431 cell migration and invasion. Preliminary experiments showing that secretion of metalloproteinases MMP2 and MMP9 by A431 tumor cells was inhibited by the purified C. sativa MGX strongly suggest that this mechanism of action may play a role in its antimigration and anti-invasive properties.

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The present study provides a theoretical description of the different levels of structural organization that characterize the xylan polysaccharide in its native and hydrophobic lauroyl esterified forms. The goal of this study was to ascertain the role played by the hydroxyl or lauroyl side groups on the conformational flexibility of the xylan chain backbone. The results reported provide a detailed description of the low-energy conformers of the dimer segments, a complete characterization of the helical structures, an insight into the disordered state of the polysaccharide chains and an estimation of the cohesion of the amorphous solids. Esterification of xylan hydroxyl groups by lauric acid has a large effect on the conformational properties of the glycosidic bonds linking two repeat units. Both the location and the relative energies of the low energy areas of the potential energy surfaces strongly differ: extended and coiled conformations are preferred for the native and hydrophobic forms, respectively. Consequently, the predicted unperturbed polymer chain extension strongly depends on the structure, predicted Lp of the native xylan of 35 A compares favourably well with the experimental ones, this characteristic dramatically decreases to 9A for the hydrophobically modified chain. Curiously, only extended 2(1) and left-handed 3(1) helical structures are calculated stable for both polymers. The estimated cohesive parameters of amorphous bulks reveal that inter-chain interactions are stronger for the xylan chain than that for modified one, the former being stabilized by hydrogen bonds whereas hydrophobic interactions play a determinant role for the latter.

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Esterification of hemicelluloses of the xylan family was performed in order to produce hydrophobic films. Acylation reactions were carried out with lauroyl chloride in the N,N-dimethylacetamide/lithium chloride homogeneous system using 4-dimethylaminopyridine as activator and were induced by microwave irradiation. In the experimental conditions used, 108 and 172% mass ratios were obtained for the dodecyl-grafted xylan and heteroxylan, respectively. The degrees of substitution (DS) were 1.3 (maximum 2) for xylan and 1.2 (maximum 2.1) for heteroxylan. These products were further characterized by FT-IR spectroscopy. The mechanical and thermomechanical behavior of this new family of hydrophobic films were analyzed and compared to those obtained from cellulose with a similar DS by the means of tensile tests. Our results indicate that the dodecyl-grafted xylan film presents the best rigidity-resistance to traction ratio.

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