Towards the Hydrophobization of Thermoplastic Starch Using Fatty Acid Starch Ester as Additive.

To bring surface hydrophobicity to thermoplastic starch (TPS) materials for food packaging, fatty acid starch esters (FASE), specifically starch tri-laurate, were incorporated into TPS formulations. A total of three different ratios of FASE (2%, 5% and 10%) were added to the TPS formulation to evaluate the influence of FASE onto physico-chemical properties of TPS/FASE blends, i.e., surface hydrophobicity, dynamic vapor sorption (DVS), and tensile behaviors. Blending TPS with FASE leads to more hydrophobic materials, whatever the FASE ratio, with initially measured contact angles ranging from 90° for the 2%-FASE blend to 99° for the 10%-blend. FT-IR study of the material surface and inner core shows that FASE is mainly located at the material surface, justifying the increase of material surface hydrophobicity. Despite this surface hydrophobicity, blending TPS with FASE seems not to affect blend vapor sorption behavior. From a mechanical behavior perspective, the variability of tensile properties of starch-based materials with humidity rate is slightly reduced with increasing FASE ratio (a decrease of maximal stress of 10-30% was observed for FASE ratio 2% and 10%), leading to more ductile materials.

Cell Wall Composition of Hemp Shiv Determined by Physical and Chemical Approaches.

The use of agricultural by-products in the building engineering realm has led to an increase in insulation characteristics of biobased materials and a decrease in environmental impact. The understanding of cell wall structure is possible by the study of interactions of chemical compounds, themselves determined by common techniques like Van Soest (VS). In this study, a global method is investigated to characterise the cell wall of hemp shiv. The cell wall molecules were, at first, isolated by fractionation of biomass and then analysed by physical and chemical analysis (Thermal Gravimetric Analysis, Elementary Analysis, Dynamic Sorption Vapor and Infra-Red). This global method is an experimental way to characterise plant cell wall molecules of fractions by Thermal Gravimetric Analysis following by a mathematical method to have a detailed estimation of the cell wall composition and the interactions between plant macromolecules. The analyzed hemp shiv presents proportions of 2.5 ± 0.6% of water, 4.4 ± 0.2% of pectins, 42.6 ± 1.0% (Hemicellulose-Cellulose), 18.4 ± 1.6% (Cellulose-Hemicellulose), 29.0 ± 0.8% (Lignin-Cellulose) and 2.0 ± 0.4% of linked lignin.

Synthetic Mono-Rhamnolipids Display Direct Antifungal Effects and Trigger an Innate Immune Response in Tomato against Botrytis Cinerea.

Natural rhamnolipids are potential biocontrol agents for plant protection against bacterial and fungal diseases. In this work, we synthetized new synthetic mono-rhamnolipids (smRLs) consisting in a rhamnose connected to a simple acyl chain and differing by the nature of the link and the length of the lipid tail. We then investigated the effects of these ether, ester, carbamate or succinate smRL derivatives on Botrytis cinerea development, symptoms spreading on tomato leaves and immune responses in tomato plants. Our results demonstrate that synthetic smRLs are able to trigger early and late immunity-related plant defense responses in tomato and increase plant resistance against B. cinerea in controlled conditions. Structure-function analysis showed that chain length of the lipidic part and type of acyl chain were critical to smRLs immune activity and to the extent of symptoms caused by the fungus on tomato leaves.

Importance of the C12 Carbon Chain in the Biological Activity of Rhamnolipids Conferring Protection in Wheat against Zymoseptoria tritici.

The hemibiotrophic fungus Zymoseptoria tritici, responsible for Septoria tritici blotch, is currently the most devastating foliar disease on wheat crops worldwide. Here, we explored, for the first time, the ability of rhamnolipids (RLs) to control this pathogen, using a total of 19 RLs, including a natural RL mixture produced by Pseudomonas aeruginosa and 18 bioinspired RLs synthesized using green chemistry, as well as two related compounds (lauric acid and dodecanol). These compounds were assessed for in vitro antifungal effect, in planta defence elicitation (peroxidase and catalase enzyme activities), and protection efficacy on the wheat-Z. tritici pathosystem. Interestingly, a structure-activity relationship analysis revealed that synthetic RLs with a 12 carbon fatty acid tail were the most effective for all examined biological activities. This highlights the importance of the C12 chain in the bioactivity of RLs, likely by acting on the plasma membranes of both wheat and Z. tritici cells. The efficacy of the most active compound Rh-Est-C12 was 20-fold lower in planta than in vitro; an optimization of the formulation is thus required to increase its effectiveness. No Z. tritici strain-dependent activity was scored for Rh-Est-C12 that exhibited similar antifungal activity levels towards strains differing in their resistance patterns to demethylation inhibitor fungicides, including multi-drug resistance strains. This study reports new insights into the use of bio-inspired RLs to control Z. tritici.

Development of curcumin-cyclodextrin/cellulose nanocrystals complexes: New anticancer drug delivery systems.

The synthesis of curcumin-cyclodextrin/cellulose nanocrystals (CNCx) nano complexes was performed. CNCx were functionalized by ionic association with cationic ß-cyclodextrin (CD) and CD/CNCx complexes were used to encapsulate curcumin. Preliminary in vitro results showed that the resulting curcumin-CD/CNCx complexes exerted antiproliferative effect on colorectal and prostatic cancer cell lines, with IC50s lower than that of curcumin alone.

Enzymatic synthesis of amphiphilic carbohydrate esters: Influence of physicochemical and biochemical parameters.

Glycolipids, carbohydrate fatty esters or sugar esters are amphiphilic molecules containing hydrophilic groups bonded to hydrophobic parent structures. Recently, glycolipids have shown their antimicrobial and antitumor capacities. Their surface activity properties have applications in the food, pharmaceutical and cosmetic industries. Sugar esters' building blocks can be obtained from natural resources and/or be transformed by biochemical pathways for uses as surfactants. Biosurfactants are non-ionic, nontoxic, biodegradable, tasteless, and odourless. The biocatalysis of these molecules involves sustainable, green, and safer methods. The advantages of producing biosurfactants from enzymatic catalysis are the energy economy, high selectivity, production of natural products, reduction of the use of fossil-based solvents and chloride compounds. This review presents the most recent studies concerning the evaluation of the impact of the main parameters and their levels influencing the enzymatic synthesis of glycolipids. Various enzyme catalysed synthetic methods were described. The parameters studied were temperature, reaction time, solvent system, type of biocatalyst, substrates molar ratio proportion and the nature of substrates. This review discusses the influence of different biocatalysts in the conversions of glycolipids; The reactivity from mono to polysaccharides and their interaction with fatty acids of different carbon chain lengths in the presence of specific enzymes; The effect of the solvent polarity, the use of multiple solvents, ionic liquids, supercritical CO2, and solvent-free media in sugar ester conversions; And the optimization of temperature and reaction time in different enzymatic systems.

Towards the synthesis of new benzimidazolone derivatives with surfactant properties.

New water-soluble benzimidazolone derivatives were synthesized. In the first approach, di-N-glycosyl and mono-N-alkyl-N-glycosyl compounds were obtained by grafting C-6-activated glycosides onto benzimidazolone. In the second approach, benzimidazolone derivatives bearing a glucosyl unit were synthesized using an efficient glycosylation method. Every compound structure was confirmed by means of NMR spectroscopy and elemental analysis. The preliminary surfactant properties of some compounds were evaluated.

Enhancement of photobactericidal activity of chlorin-e6-cellulose nanocrystals by covalent attachment of polymyxin B.

Despite the advances made over the last decade, infections caused by multi-drug resistant bacterial strains are increasingly important societal issues that need to be addressed. New approaches have already been developed in order to overcome this problem. Photodynamic antimicrobial chemotherapy (PACT) could provide an alternative to fight infectious bacteria. This approach has already inspired the development of innovative materials. Interesting results have been obtained against Gram-positive bacteria, but it also appeared that Gram-negative strains, especially Pseudomonas aeruginosa, were less sensitive to PACT. Enhanced efficacy against Gram-negative bacteria had been previously obtained with photosensitizers bound to antimicrobial peptides. In this work, we designed a photobactericidal organic material, CNCsc6-PMB, consisting of cellulose nanocrystals to which the photosensitizer chlorin-e6 and the antimicrobial polypeptide polymyxin B (PMB) were covalently attached. These modified nanocrystals were characterized by IR spectroscopy, zeta potential measurements and elemental analyses, after which antibacterial assays were carried out. Following light irradiation, CNCsc6-PMB demonstrated efficiency against Gram-negative bacteria (Escherichia coli and Pseudomonas aeruginosa) and Gram-positive bacteria (Staphylococcus aureus and Staphylococcus epidermidis) by inhibition of bacterial growth. An amplifying effect of chlorin-e6 has been highlighted against these Gram-negative strains, based on membrane weakening and a potential docking effect from the polymyxin moiety. Such results confirmed the importance of using an antimicrobial peptide in order to broaden the spectrum of PACT.

Adamantoylated monosaccharides: new compounds for modification of the properties of cyclodextrin-containing materials.

Adamantoyl glycosides were obtained in good yields by coupling adamantanecarboxylic acid with monosaccharides. They form very stable inclusion complexes with beta-cyclodextrin, as shown by (1)H NMR measurements.

Synthesis of chacotriose analogues.

We report here the synthesis of three chacotriose analogues, namely beta-L-fucopyranosyl-(1-->2)-[beta-L-fucopyranosyl-(1-->4)]-D-glucopyranose, beta-L-fucopyranosyl-(1-->2)-[beta-L-fucopyranosyl-(1-->4)]-d-galactopyranose, and alpha-L-rhamnopyranosyl-(1-->2)-[alpha-L-rhamnopyranosyl-(1-->4)]-alpha-D-galactopyranose.

Structural reinvestigation of the core oligosaccharide of a mutant form of Aeromonas salmonicida lipopolysaccharide containing an O-4 phosphorylated and O-5 substituted Kdo reducing end group using electrospray QqTOF-MS/MS.

The molecular structure of the mutant form of the lipopolysaccharide of Aeromonas salmonicida was determined to contain an O-4 phosphorylated and O-5 substituted Kdo reducing group, and is proposed as the following: [molecular structure: see text] It was established that during the cleavage of this LPS with 1% acetic acid, to release the core oligosaccharide from the Lipid A portion, we obtained a degraded core oligosaccharide which eliminated its phosphate group with extreme facility. The precise molecular structure of this dephosphorylated core was deduced by electrospray mass spectrometry and is proposed as the following:[molecular structure: see text] Low energy collision ESI-QqTOF-MS/MS analysis of the dephosphorylated core oligosaccharide confirmed the presence of the O-5 glycosylated 4,8- and 4,7-anhydro derivatives of the enolizable alpha-keto-acids. The CID tandem mass spectrometric analysis of the heterogeneous mixture of the permethylated core oligosaccharide established the unreported methylation reaction on the diastereomeric 4,8- and 4,7-anhydro alpha-keto-acids and the complete permethylation and addition reaction of the O-5 glycosylated open chain reducing end terminal D-arabino-3-en-2-ulonic acid. The stereo-specific fragmentation routes obtained during the tandem mass spectrometric analysis permitted the precise sequencing of this dephosphorylated rough core oligosaccharide of the mutant LPS of A. salmonicida.

Evidence of a self-inclusion phenomenon for a new class of mono-substituted alkylammonium-beta-cyclodextrins.

A new class of mono-substituted N-alkyl-N,N-dimethylammonium-beta-cyclodextrins has been synthesized in a three step procedure from the native beta-cyclodextrin. The structural analysis of these compounds undertaken by combined use of 1D and 2D NMR spectra indicate that the two methyl groups bound on the nitrogen are magnetically inequivalent due to a self-inclusion phenomenon of the alkyl chain inside the CD cavity. A variable-temperature 1H NMR study showed that these mono-substituted CD derivatives formed temperature-independent intramolecular complexes with their own alkylammonium substituent. The strength of the interaction between the alkyl moiety and the cyclodextrin cavity has been evaluated by a competitive method using an adamantane derivative. Finally, surface tension measurements demonstrated the surface active character of these compounds and confirmed their self-inclusion ability.