L-Rhamnose and Phenolic Esters-Based Monocatenar and Bolaform Amphiphiles: Eco-Compatible Synthesis and Determination of Their Antioxidant, Eliciting and Cytotoxic Properties.

Symmetrical and dissymmetrical bolaforms were prepared with good to high yields from unsaturated L-rhamnosides and phenolic esters (ferulic, phloretic, coumaric, sinapic and caffeic) using two eco-compatible synthetic strategies involving glycosylation, enzymatic synthesis and cross-metathesis under microwave activation. The plant-eliciting activity of these new compounds was investigated in Arabidopsis model plants. We found that the monocatenar rhamnosides and bolaforms activate the plant immune system with a response depending on the carbon chain length and the nature of the hydrophilic heads. Their respective antioxidant activities were also evaluated, as well as their cytotoxic properties on dermal cells for cosmetic uses. We showed that phenolic ester-based compounds present good antioxidant activities and that their cytotoxicity is low. These properties are also dependent on the carbon chains used.

Encapsulation of Vitamin C by Glycerol-Derived Dendrimers, Their Interaction with Biomimetic Models of Stratum corneum and Their Cytotoxicity.

Vitamin C is one of the most sensitive cosmetic active ingredients. To avoid its degradation, its encapsulation into biobased carriers such as dendrimers is one alternative of interest. In this work, we wanted to evaluate the potential of two biobased glycerodendrimer families (GlyceroDendrimers-Poly(AmidoAmine) (GD-PAMAMs) or GlyceroDendrimers-Poly(Propylene Imine) (GD-PPIs)) as a vitamin C carrier for topical application. The higher encapsulation capacity of GD-PAMAM-3 compared to commercial PAMAM-3 and different GD-PPIs, and its absence of cytotoxicity towards dermal cells, make it a good candidate. Investigation of its mechanism of action was done by using two kinds of biomimetic models of stratum corneum (SC), lipid monolayers and liposomes. GD-PAMAM-3 and VitC@GD-PAMAM-3 (GD-PAMAM-3 with encapsulated vitamin C) can both interact with the lipid representatives of the SC lipid matrix, whichever pH is considered. However, only pH 5.0 is suggested to be favorable to release vitamin C into the SC matrix. Their binding to SC-biomimetic liposomes revealed only a slight effect on membrane permeability in accordance with the absence of cytotoxicity but an increase in membrane rigidity, suggesting a reinforcement of the SC barrier property. Globally, our results suggest that the dendrimer GD-PAMAM-3 could be an efficient carrier for cosmetic applications.

Essential Oil-Based Bioherbicides: Human Health Risks Analysis.

In recent years, the development of new bio-based products for biocontrol has been gaining importance as it contributes to reducing the use of synthetic herbicides in agriculture. Conventional herbicides (i.e., the ones with synthetic molecules) can lead to adverse effects such as human diseases (cancers, neurodegenerative diseases, reproductive perturbations, etc.) but also to disturbing the environment because of their drift in the air, transport throughout aquatic systems and persistence across different environments. The use of natural molecules seems to be a very good alternative for maintaining productive agriculture but without the negative side effects of synthetic herbicides. In this context, essential oils and their components are increasingly studied in order to produce several categories of biopesticides thanks to their well-known biocidal activities. However, these molecules can also be potentially hazardous to humans and the environment. This article reviews the state of the literature and regulations with regard to the potential risks related to the use of essential oils as bioherbicides in agricultural and horticultural applications.

Encapsulation of Essential Oils for the Development of Biosourced Pesticides with Controlled Release: A Review.

Essential oil (EO) encapsulation can be carried out via a multitude of techniques, depending on applications. Because of EOs' biological activities, the development of biosourced pesticides with EO encapsulation is of great interest. A lot of methods have been developed; they are presented in this review, together with the properties of the final products. Encapsulation conserves and protects EOs from outside aggression, but also allows for controlled release, which is useful for applications in agronomy. The focus is on the matrices that are of interest for the controlled release of their content, namely: alginate, chitosan, and cyclodextrin. Those three matrices are used with several methods in order to create EO encapsulation with different structures, capacities, and release profiles.

Differential Interaction of Synthetic Glycolipids with Biomimetic Plasma Membrane Lipids Correlates with the Plant Biological Response.

Natural and synthetic amphiphilic molecules including lipopeptides, lipopolysaccharides, and glycolipids are able to induce defense mechanisms in plants. In the present work, the perception of two synthetic C14 rhamnolipids, namely, Alk-RL and Ac-RL, differing only at the level of the lipid tail terminal group have been investigated using biological and biophysical approaches. We showed that Alk-RL induces a stronger early signaling response in tobacco cell suspensions than does Ac-RL. The interactions of both synthetic RLs with simplified biomimetic membranes were further analyzed using experimental and in silico approaches. Our results indicate that the interactions of Alk-RL and Ac-RL with lipids were different in terms of insertion and molecular responses and were dependent on the lipid composition of model membranes. A more favorable insertion of Alk-RL than Ac-RL into lipid membranes is observed. Alk-RL forms more stable molecular assemblies than Ac-RL with phospholipids and sterols. At the molecular level, the presence of sterols tends to increase the RLs' interaction with lipid bilayers, with a fluidizing effect on the alkyl chains. Taken together, our findings suggest that the perception of these synthetic RLs at the membrane level could be related to a lipid-driven process depending on the organization of the membrane and the orientation of the RLs within the membrane and is correlated with the induction of early signaling responses in tobacco cells.

Click reactions as a key step for an efficient and selective synthesis of D-xylose-based ILs.

D-Xylose-based ionic liquids have been prepared from D-xylose following a five steps reaction sequence, the key step being a click cycloaddition. These ionic liquids (ILs) have been characterized through classical analytical methods (IR, NMR, mass spectroscopy, elemental analysis) and their stability constants, Tg and Tdec, were also determined. Considering their properties and their hydrophilicity, these compounds could be alternative solvents for chemical applications under mild conditions.

Bolaamphiphiles derived from alkenyl L-rhamnosides and alkenyl D-xylosides: importance of the hydrophilic head.

The two step synthesis of a new bolaamphiphile derived from alkenyl L-rhamnosides was described. The general synthetic strategy of bolaamphiphiles derived from L-rhamnose was based on a previous work describing the synthesis of bolaamphiphiles derived from D-xylose. The conformational properties of this new compound were investigated by FTIR spectroscopy in an aqueous film in order to obtain a reference for further studies about the membrane-interacting properties. Moreover, the surface activity of this new bolaamphiphile was analyzed by Langmuir balance technology and was compared with that of the analogous bolaamphiphile derived from alkenyl D-xylosides. The findings indicate that the rhamnoside-based bolaform has an increased surface activity and a better ability to form aggregates than xyloside-based one.

Melt processing of paramylon using a water:ionic liquid mixture as plasticizer.

Paramylon is a linear ß-1,3-glucan produced by the microalgae Euglena Gracilis. Due to its native crystalline structure, involving hexagonally packed triple helices, paramylon is neither water soluble nor thermoplastic. While such properties are generally obtained by chemical modification of paramylon, the present work demonstrates that using ionic liquid/water mixtures as solvents or plasticizers may be an alternative: A mixture of water with cholinium glycinate (40:60) allowed: i) obtaining paramylon solutions at 80 °C, that form reversible ionogels upon cooling at 20 °C, when used as a solvent, and ii) the thermomechanical processing of paramylon below 100 °C by extrusion and hot-press into transparent films, when used as a plasticizer. The thermoplastic paramylon obtained consists of an amorphous matrix, self-reinforced by oriented triple helices packed as nanofibers. This results in a storage modulus ranging from 300 to 450 MPa at 25 °C, depending on the plasticizer content, and in a tensile strain at break of 27 %. For storage times larger than 1 month, a recrystallization of paramylon is observed, with an unidentified crystalline structure different from the native one. Recrystallized samples can be reprocessed into amorphous films by hot pressing.

A review of paramylon processing routes from microalga biomass to non-derivatized and chemically modified products.

Paramylon is a linear ß-1,3-glucan, similar to curdlan, produced as intracellular granules by the microalga Euglena gracilis, a highly versatile and robust strain, able to grow under various trophic conditions, with valorization of CO2, wastewaters, or food byproducts as nutrients. This review focuses in particular on the various processing routes leading to new potential paramylon based products. Due to its crystalline structure, involving triple helices stabilized by internal intermolecular hydrogen bonds, paramylon is neither water-soluble nor thermoplastic. The few solvents able to disrupt the triple helices, and to fully solubilize the polymer as random coils, allow non derivatizing shaping into films, fibers, and even nanofibers by a specific self-assembly mechanism. Chemical modification in homogeneous or heterogeneous conditions is also possible. The non-selective or regioselective substitution of the hydroxyl groups of glucosidic units leads to water-soluble ionic derivatives and thermoplastic paramylon esters with foreseen applications ranging from health to bioplastics.

Cinnamomum zeylanicum Essential Oil Formulation with Poly(propylene imine) Dendrimers with Surface-Grafted Glycerol: Release Kinetics of trans-Cinnamaldehyde and Germination Inhibition Effects.

The Third-generation glycerodendrimer polypropylenimine (GD-PPI-3) can be used in an aqueous formulation of Cinnamomum zeylanicum essential oil (CEO). The purpose was to give an overview of this innovative method of retaining and releasing essential oils. The formulation consisted of 366 min stirring at 1735 rpm of the aqueous solution of 2 mM GD-PPI-3 with CEO. Some physicochemical properties of these formulations, as well as the release of trans-cinnamaldehyde, have been studied. A bimodal distribution and no concentration or aging effect were observed by optical microscopy. Moreover, the release kinetics showed the retention of volatile molecules in solution under various environmental conditions. The release profile was characterized by an initial burst followed by a steady release. The dendrimers allowed us to reduce this initial burst and extended the release by at least 15 h. In addition, the herbicidal effect was evaluated: inhibition of Arabidopsis thaliana seed germination was obtained for 7 days with a formulation of 12.5 mg/L CEO in a closed space and 360 mg/L CEO in an open space.

Preparation of New Glycerol-Based Dendrimers and Studies on Their Behavior toward Essential Oil Encapsulation.

Two new families of glycerol-based dendrimers (glyceroladendrimers (GADs) and glyceroclickdendrimers (GCDs)) have been synthesized. Three generations have been isolated for each family with good yields and were fully analyzed. The encapsulation of essential oils (citronella and cinnamon) in GADs, GCDs, and also in previously described glycerodendrimers GD-PAMAMs and GD-PPIs has been studied by dynamic-headspace gas chromatography coupled to mass spectrometry. The retention rates obtained were from -35.8 to 26.65% for citronella essential oil and from 2.14 to 38.84% for the cinnamon essential oil. In addition, the best results were obtained with GD-PAMAMs and GD-PPIs of higher generation. The interaction study between essential oils or more precisely their major components have been performed through NMR spectroscopy (1H NMR and DOSY NMR). No direct interactions between dendrimers and essential oils have been observed, but a surprising behavior of compression of the dendrimer in stable emulsions was observed. Indeed, the hydrodynamic radius of GD-PPI-3 has been reduced in the presence of cinnamon essential oil.

Synthesis and Activity of Ionic Antioxidant-Functionalized PAMAMs and PPIs Dendrimers.

For this study, new dendrimers were prepared from poly(propylene imine) (PPI) and polyamidoamine (PAMAM) dendrimers using an efficient acid-base reaction with various phenolic acids. The syntheses were also optimized in both microwave and microfluidic reactors. These ionic and hydrophilic dendrimers were fully characterized and showed excellent antioxidant properties. Their cytotoxic properties have been also determined in the case of fibroblast dermal cells.

Use of New Glycerol-Based Dendrimers for Essential Oils Encapsulation: Optimization of Stirring Time and Rate Using a Plackett-Burman Design and a Surface Response Methodology.

Essential oils are used in an increasing number of applications including biopesticides. Their volatility minimizes the risk of residue but can also be a constraint if the release is rapid and uncontrolled. Solutions allowing the encapsulation of essential oils are therefore strongly researched. In this study, essential oils encapsulation was carried out within dendrimers to control their volatility. Indeed, a spontaneous complexation occurs in a solution of dendrimers with essential oils which maintains it longer. Six parameters (temperature, stirring rate, relative concentration, solvent volume, stirring time, and pH) of this reaction has been optimized by two steps: first a screening of the parameters that influence the encapsulation with a Plackett-Burmann design the most followed by an optimization of those ones by a surface response methodology. In this study, two essential oils with herbicide properties were used: the essential oils of Cinnamomum zeylanicum Blume and Cymbopogon winterianus Jowitt; and four biosourced dendrimers: glycerodendrimers derived from polypropylenimine and polyamidoamine, a glyceroclikdendrimer, and a glyceroladendrimer. Meta-analysis of all Plackett-Burman assays determined that rate and stirring time were effective on the retention rate thereby these parameters were used for the surface response methodology part. Each combination gives a different optimum depending on the structure of these molecules.

Palladium-catalyzed telomerization of butadiene with polyols: from mono to polysaccharides.

The telomerization of butadiene with alcohols is an elegant way to synthesize ethers with minimal environmental impact since this reaction is 100% atom efficient. Besides telomerization of butadiene with methanol and water that is industrially developed, the modification of polyols is still under development. Recently, a series of new substrates has been involved in this reaction, including diols, pure or crude glycerol, protected or unprotected monosaccharides, as well as polysaccharides. This opens up the formation of new products having specific physicochemical properties. We will describe recent advances in this field, focusing on the reaction of renewable products and more specifically on saccharides. The efficient catalytic systems as well as the optimized reaction conditions will be described and some physicochemical properties of the products will be reported.

"Click" glycodendrimers containing 27, 81, and 243 modified xylopyranoside termini.

A series of large glycodendrimers containing 27, 81, and 243 terminal modified xylose branches from the first (G(1)-27) to the third generation (G(3)-243) were synthesized from 2'-azidoethyl 2,3,4-tri-O-acetyl-beta-d-xylopyranoside and alkynyl-terminated dendrimers by "click" chemistry that is confirmed to be an excellent method to obtain large glycodendrimers exemplified by the use of modified xylose. The dendrimers were first characterized by (1)H NMR, (13)C{(1)H} NMR, elemental analysis, and IR spectroscopy. The size progression in the series was also demonstrated using both DOSY NMR and size exclusion chromatography (SEC), the latter technique showing the good polydispersity of all the dendrimers. The size measured by dynamic light scattering (DLS) for the dendrimer G(3)-243 is close to that obtained by the DOSY NMR method.

Synthetic Rhamnolipid Bolaforms trigger an innate immune response in Arabidopsis thaliana.

Stimulation of plant innate immunity by natural and synthetic elicitors is a promising alternative to conventional pesticides for a more sustainable agriculture. Sugar-based bolaamphiphiles are known for their biocompatibility, biodegradability and low toxicity. In this work, we show that Synthetic Rhamnolipid Bolaforms (SRBs) that have been synthesized by green chemistry trigger Arabidopsis innate immunity. Using structure-function analysis, we demonstrate that SRBs, depending on the acyl chain length, differentially activate early and late immunity-related plant defense responses and provide local increase in resistance to plant pathogenic bacteria. Our biophysical data suggest that SRBs can interact with plant biomimetic plasma membrane and open the possibility of a lipid driven process for plant-triggered immunity by SRBs.

Alkenyl and alkenoyl amphiphilic derivatives of D-xylose and their surfactant properties.

Unsaturated fatty alkyl xylosides and the corresponding 1-O-acyl esters were prepared. Critical micellar concentrations, surface tension areas per molecule and foaming value of some of these new amphiphilic compounds have been determined.

Neutral pentosides surfactants issued from the butadiene telomerization with pentoses: preparation and amphiphilic properties.

Interfacial properties of octadienyl pentosides prepared by the palladium-catalyzed telomerization of butadiene with free pentoses have been evaluated and compared to those of mixtures issued from the autoclaving process.

Interactions of sugar-based bolaamphiphiles with biomimetic systems of plasma membranes.

Glycolipids constitute a class of molecules with various biological activities. Among them, sugar-based bolaamphiphiles characterized by their biocompatibility, biodegradability and lower toxicity, became interesting for the development of efficient and low cost lipid-based drug delivery systems. Their activity seems to be closely related to their interactions with the lipid components of the plasma membrane of target cells. Despite many works devoted to the chemical synthesis and characterization of sugar-based bolaamphiphiles, their interactions with plasma membrane have not been completely elucidated. In this work, two sugar-based bolaamphiphiles differing only at the level of their sugar residues were chemically synthetized. Their interactions with membranes have been investigated using model membranes containing or not sterol and with in silico approaches. Our findings indicate that the nature of sugar residues has no significant influence for their membrane interacting properties, while the presence of sterol attenuates the interactions of both bolaamphiphiles with the membrane systems. The understanding of this distinct behavior of bolaamphiphiles towards sterol-containing membrane systems could be useful for their applications as drug delivery systems.

Synthesis of chiral ß-aminoalcohol palladium complexes exhibiting cytotoxic properties.

Original palladium complexes involving (-)-ephedrine, (-)-norephedrine, L-prolinol, L-valinol and L-isoleucinol have been rapidly prepared in neutral or basic medium and simply purified. They have been fully characterized by classical analytical methods and four of them were characterized by X-Ray analysis. In parallel with the experimental work, HF-DFT(B3LYP/PCM) computations were performed to obtain additional structural information. Their antiproliferative properties have been evaluated and some complexes showed small activities especially towards HT29 human cancer cells.