Amphiphilic structure-surface property relationships of monosaccharide-based surfactants

Poster (2013, April 08)

A set of monosaccharide-based renewable surfactants has been prepared, structurally checked, and systematically screened for different activities and functionalities. These compounds vary in the polar ... [more ▼]

A set of monosaccharide-based renewable surfactants has been prepared, structurally checked, and systematically screened for different activities and functionalities. These compounds vary in the polar head group, linker, and hydrophobic tail. Beyond the goal to find out the most potential valuable surfactants for each measurement, relationships between chemical structure, basic properties, and functionalities have been examined by comparing compounds differing in a single structural variable. In this paper, we show and explain the impact of the anomeric alpha or bêta, neutral or acid sugar derivatives, equatorial or axial position of hydroxyl group, alkyl chain substitute attachment position, number, and length on surface properties of sugar-based surfactants. [less ▲]

Enzymatic synthesis, surface and lipid interaction properties of novel rhamnolipids

Conference (2013)

Amongst glycolipidid biosurfactants, rhamnolipids have drawn particular attention as they have several interesting biological properties such as antimicrobial, antiphytoviral, zoosporicidal and plant ... [more ▼]

Amongst glycolipidid biosurfactants, rhamnolipids have drawn particular attention as they have several interesting biological properties such as antimicrobial, antiphytoviral, zoosporicidal and plant defense elicitor activities [1-3]. It is generally recognised that these activities must be linked to the interaction of these molecules with constituents of biological membranes [4] but the detailed mechanism is far from being fully understood. The objective of this work is double. First, it aims to investigate a new strategy of synthesis for the production of novel rhamnolipids [5] that could exhibit properties as promising for industrial and environmental applications as their natural counterparts while avoiding the use of the pathogenic Pseudomonas aeruginosa for their production. Secondly, their basic surface properties (critical aggregation concentration, surface tension at CAC and interfacial behaviour of their monolayer) and their interaction with model membranes are investigated in relation with their structure in order to give insight about the mechanism of their biological actions. [1] Vatsa P. et al. Int. J. Mol. Sci. 2010;11:5095. [2] Varnier A-L. et al. Plant, Cell Environ. 2009;32:178. [3] Lang S. et al. Appl. Microbiol. Biotechn. 1999;51:22. [4] Aranda F.J. et al. Langmuir. 2007;23:2700. [5] Nott K. et al. Process Biochemistry, http://dx.doi.org/10.1016/j.procbio.2012.11.019 [less ▲]

Green synthesis and antioxidant activity of new PEGylated ferulic acids

in Tetrahedron Letters (2012), 53(19), 2402-2405

PEGylation of ferulic acid is described through a green esterification process involving poly(ethylene glycol) (PEG) with three different average molecular weights (200, 400 and 1000 g/mol) as both ... [more ▼]

PEGylation of ferulic acid is described through a green esterification process involving poly(ethylene glycol) (PEG) with three different average molecular weights (200, 400 and 1000 g/mol) as both reactive and solvent. Esterification with PEG400 and PEG1000 leads to original compounds soluble in all proportions in water. These new compounds display an antioxidant activity similar to that of ferulic acid. [less ▲]

(Trans)esterification of mannose catalyzed by lipase B from Candida antarctica in an improved reaction medium using co-solvents and molecular sieve

in Preparative Biochemistry & Biotechnology (2012), 42(4), 348-363

Structure-Surface Activity Relationships Of Uronic Acid-Derivative Surfactants From Renewable Resources Applications

Poster (2011, June)

Introduction and Background: Uronic acid-derivative surfactants are amphiphilic compounds with growing interests owing to their potential applications in various areas [1]. This class of carbohydrate ... [more ▼]

Introduction and Background: Uronic acid-derivative surfactants are amphiphilic compounds with growing interests owing to their potential applications in various areas [1]. This class of carbohydrate-based surfactants can be easily prepared from renewable raw materials in a wide range of structure by modular synthesis thanks to the presence of one carboxylic and numerous hydroxyl groups. The polar head group configurations according to the stereochemistry of OH groups, and geometry (cyclic or not), the hydrophobic tail (number and length of alkyl chain), and the type of linker (ester, acetal and amide, etc) are among the main variables in their structural entities. Therefore, the investigation of their structure-surface activity relationships appears valuable for increasing backgrounds, and achieving a rational design for selecting the best structures to be used in different industrial fields [2]. Methodology: A few analogous of glucuronic acid-derivative surfactants have been synthesized by chemical or enzymatic routes. After purification, their structure has been confirmed by various spectroscopic techniques (RMN, MS, IR). Surface tensions of true aqueous solution have been then measured in dynamic and static modes using a series of complementary techniques. Critical micelle concentrations, minimum molecular areas, and maximum surface excesses have also been determined. Results and Discussion: Glucuronic acid derivative surfactants under investigation vary in the polar head group configuration including cyclic or non-cyclic structure and α or β anomeric form, in the hydrophobic tail regarding to the chain length (C8 to C14), the presence of a double bond, as well as an OH group at the terminal carbon, and in the type of linker, ester in C6 or acetal in C1. Results showed that all of these structural attributes affect both dynamic and equilibrium surface properties of glucuronic acid -based surfactants. Conclusion: A set of synthetic glucuronic acid-based surfactants varying in the polar head group, hydrophobic tail, and linker allow us to generate various surface-active properties at the air-water interface, and to increase the knowledge on relationships between their structure and surface-active properties. [1] Laurent, P.; Razafindralambo, H.; Wathelet, B.; Blecker, C.; Wathelet, J.-P.; Paquot, M., Synthesis and Surface-Active Properties of Uronic Amide Derivatives, Surfactants from Renewable Organic Raw Materials. Journal of Surfactants and Detergents 2010, in press. [2] Razafindralambo, H.; Blecker, C.; Mezdour, S.; Deroanne, C.; Crowet, J.; Brasseur, R.; Lins, L.; Paquot, M., Impacts of the Carbonyl Group Location of Ester Bond on Interfacial Properties of Sugar-Based Surfactants: Experimental and Computational Evidences. The Journal of Physical Chemistry B 2009, 113 (26), 8872-8877. Acknowledgment: This work was supported by Belgian Walloon Region within DGTRE research project of excellence (TECHNOSE). [less ▲]

Influence of co-solvents and molecular sieve on mannose enzymatic acylation.

Poster (2010, October 14)

CARBOHYDRATE-BASED SURFACTANTS FOR FORMING AND STABILIZING COLLOIDAL SYSTEMS AS EMULSIONS AND FOAMS

in Abstracts book of 5th edition of world congress on emulsions (2010, October 12)

Carbohydrate-based surfactants (CBS) constitute a class of amphiphilic molecules with particular and common interests. These surface-active compounds can be produced from the most abundant renewable ... [more ▼]

Carbohydrate-based surfactants (CBS) constitute a class of amphiphilic molecules with particular and common interests. These surface-active compounds can be produced from the most abundant renewable materials allowing large product concept possibilities, and may occur in a large structural range with one or more hydrophilic head groups and hydrophobic chains with various linkers/spacers, thanks to numerous reactive functional groups in their basic structure. It is then possible to design a quasi-unlimited number of new compounds by (bio)-synthesis from various raw materials. This structural diversity can generate a wide range of properties, which could be developed in food and non-food applications. Our challenge is now to find out the most suitable molecular structures for the post-development of CBS, mainly for colloidal systems like emulsion, foam, and suspension. A pre-screening of the dynamic and equilibrium interfacial tensions and interfacial rheology properties of various CBS prepared by chemical, enzymatic, or chemo-enzymatic synthesis routes from the derivatives of bio-renewable substrates is carried out. Then, the characterization of emulsifying and foaming properties of pre-selected molecules is performed. These investigations are completed by the characterization of thermal properties of liquid suspensions and powders. Homologous series of two derivative compounds of glucuronic and galacturonic acids with mono- or bicatenar hydrophobic chains and different linkages (linear or cyclic ester, amide) have been chosen as CBS starting compounds. These were full characterized by spectroscopic techniques (RMN, SM, IR). The effect of the hydrophobic chain length and number, polar head group, and the linker on whole properties investigated is easily deduced. [less ▲]

Influence de l'ajout de co-solvant pour l'estérification du D-mannose et de l'acide D-glucuronique assistée par les lipases

Poster (2010, May)

En parallèle à la production de biocarburant, le second objectif du bioraffinage est la transformation des sucres issus de l’hydrolyse de la lignocellulose en produits d’intérêt, qui se substitueront aux ... [more ▼]

En parallèle à la production de biocarburant, le second objectif du bioraffinage est la transformation des sucres issus de l’hydrolyse de la lignocellulose en produits d’intérêt, qui se substitueront aux produits de la vie courante issus du pétrole. L’une des voies de valorisation envisageable est la synthèse de molécules amphiphiles par greffage de chaînes grasses sur le sucre. Ces composés trouveraient alors des applications dans de très nombreux domaines utilisant les tensioactifs (alimentaire, détergence, peinture,…) . Dans le cadre du programme d’excellence TECHNOSE et du projet d’Action de Recherche Concertées SUPERZYM, deux sucres ont été testés : un polyol, le D-mannose, et un sucre acide, l’acide D-glucuronique. Afin de conférer un caractère amphiphile à la molécule, les lipases ont été utilisées en tant qu’outils d’estérification. Ces triglycérides hydrolases sont en effet capables de catalyser ce type de réaction, et de nombreux exemples dans la littérature démontrent le fort potentiel industriel de ces enzymes , . L’estérification du D-mannose et de l’acide D-glucuronique a donc été mise en œuvre en présence de la lipase de Candida antarctica B (Novozyme 435). La réaction est effective, mais l’ajout de co-solvants tels que la pyridine ou le DMSO améliore les vitesses initiales et les rendements de la réaction. Ces améliorations seront discutées et comparées sur ce poster. [less ▲]

Towards the synthesis of mannose derovatives of natural phenolic compounds

Poster (2010)

Optimisation de l'acylation enzymatique du mannose par l'utilisation de co-solvants

Poster (2009, October 15)

Les esters de sucres sont des surfactants non-ioniques avec de nombreuses applications dans l’industrie alimentaire et pharmaceutique. La synthèse enzymatique est généralement préférée à la synthèse ... [more ▼]

Les esters de sucres sont des surfactants non-ioniques avec de nombreuses applications dans l’industrie alimentaire et pharmaceutique. La synthèse enzymatique est généralement préférée à la synthèse chimique. En effet, cette dernière consomme beaucoup d’énergie, est moins sélective envers les différents groupes hydroxyle du sucre et conduit à des produits de caramélisation. Le type de solvant, le ratio sucre / lipide, la température et le type de lipase immobilisée peuvent être modifiés afin d’optimiser la vitesse initiale et le rendement de réaction. Les travaux décrits rapportent l’optimisation de la synthèse enzymatique de myristate de mannosyle à partir de mannose et d’acide myristique en présence de la lipase de Candida antarctica B (Novozyme 435). Les concentrations optimales en mannose et en acide myristique sont respectivement de 0,1 et 0,6 M dans du tert-butanol pur à 60°C. Ces conditions conduisent à une vitesse initiale de 1,3 g/l.h pour 2 g/l d’enzyme et à un rendement molaire de 55%. Afin d’améliorer cette vitesse initiale de réaction, différents mélanges de tert-butanol et de co-solvants polaires ont été testés. Les solvants polaires (log P faibles) augmentent la solubilité des sucres mais provoquent l’inactivation partielle des lipases. Lorsque le log P est supérieur à 3, l’enzyme reste active mais ce type de milieu n’est pas approprié si les deux substrats diffèrent grandement en terme de polarité. Le but de cette étude est donc de trouver un compromis entre la solubilité du sucre et le maintient de l’activité enzymatique. Les quatre co-solvants testés sont le DMSO, le DMF, le formamide et la pyridine. Au terme de ce travail, le DMSO, à raison de 10 % dans le milieu réactionnel, s’est avéré être le meilleur co-solvant parmi ceux testés. Dans ces conditions, la vitesse initiale de réaction est accrue de 130 %. [less ▲]