Sugar-Based Surfactants: Effects of Structural Features on the Physicochemical Properties of Sugar Esters and Their Comparison to Commercial Octyl Glycosides.

Two series of sugar esters with alkyl chain lengths varying from 5 to 12 carbon atoms, and with a head group consisting of glucose or galactose moieties, were synthesized. Equilibrium surface tension isotherms were measured, yielding critical micellar concentration (CMC) surface tensions at CMC (γcmc) and minimum areas at the air-water interface (Amin). In addition, Krafft temperatures (Tks) were measured to characterize the ability of molecules to dissolve in water, which is essential in numerous applications. As a comparison to widely used commercial sugar-based surfactants, those measurements were also carried out for four octyl d-glycosides. Impacts of the linkages between polar and lipophilic moieties, alkyl chain lengths, and the nature of the sugar head group on the measured properties were highlighted. Higher Tk and, thus, lower dissolution ability, were found for methyl 6-O-acyl-d-glucopyranosides. CMC and γcmc decreased with the alkyl chain lengths in both cases, but Amin did not appear to be influenced. Both γcmc and Amin appeared independent of the ester group orientation. Notably, alkyl (methyl α-d-glucopyranosid)uronates were found to result in noticeably lower CMC, possibly due to a closer distance between the carbonyl function and the head group.

Monitoring the formation kinetics of a bicontinuous microemulsion.

HYPOTHESES: The performance of bicontinuous microemulsions is usually assessed on the characteristics of the middle phase at equilibrium. However, applied to Enhanced Oil Recovery, such an evaluation would not be representative of the structure and composition of fluids in reservoir rocks. Studies on the properties of non-equilibrated microemulsions are still needed to better understand the formation of such complex systems, in particular to optimize input parameters of process simulation tools. EXPERIMENTS: For this purpose, we monitored the formation of a microemulsion from contact with the oil to equilibrium when no mixing or convection is provided. Non-destructive methods such as Nuclear Magnetic Resonance, Micro-Computed Tomography, Dynamic Light Scattering and Small Angle X-ray scattering were used to extract the compositions, phase thicknesses, dynamics and structures of the system over time. FINDING: We found that the system gets structured into several layers over time that include the transient presence of an oriented semi-crystalline phase. The growth of the bicontinuous middle phase results from a progressive reorganization of the liquid crystal. The compositional and structural gradients, observed along the sample height, are correlated and linked to the corresponding structures of the phase diagram of the quaternary system. Equilibrium is reached after the total transfer of the liquid crystal into the bicontinuous phase.

Impact of the chemical structure on amphiphilic properties of sugar-based surfactants: A literature overview.

In this review, structure-property trends are systematically analyzed for four amphiphilic properties of sugar-based surfactants: critical micelle concentration (CMC), its associated surface tension (γCMC), efficiency (pC20) and Krafft temperature (TK). First, the impact on amphiphilic properties of the alkyl chain size and the presence of branching and/or unsaturation is investigated. Then, various polar head parameters are explored, such as the degree of polymerization of the sugar unit (mono- or oligosaccharides), the chemical nature of the linker and the sugar configuration. Some systematic comparisons between ethoxylated surfactants and sugar-based surfactants are also carried out. While some structural trends with the impact of alkyl chain length or the polar head size are now well understood, this analysis points out that systematic studies of more specific effects of alkyl chain (e.g. branching, unsaturation, presence of rings, position on the polar head) and polar head (e.g. linker, anomeric configuration, internal stereochemistry, cyclic vs. acyclic sugar residues) were scarcer or not available to date. This work encourages the use of these structural trends in the perspective of developing new bio-based surfactants and their consideration in predictive models. It also highlights the need of further experimental tests to fill remaining gaps notably to explore some specific structural features (such as the introduction of rings in the alkyl chain or the position of the alkyl chain on the polar head) and towards applicative properties (like foaming capacity or wettability).

Catalytic Synthesis of a New Series of Alkyl Uronates and Evaluation of Their Physicochemical Properties.

Large quantities (>3 g) of a new series of alkyl uronates were synthesized in two steps from commercial methyl hexopyranosides. Firstly, several tens of grams of free methyl α-d-glucopyranoside were selectively and quantitatively oxidized into corresponding sodium uronate using 2,2,6,6-tetramethyl-1-piperidinyloxy free radical (TEMPO)-catalyzed oxidation. Hydrophobic chains of different length were then introduced by acid-mediated esterification with fatty alcohols (ethyl to lauryl alcohol) leading to the desired alkyl glucuronates with moderate to good yields (49%-72%). The methodology was successfully applied to methyl α-d-mannopyranoside and methyl ß-d-galactopyranoside. Physicochemical properties, such as critical micelle concentration (CMC), equilibrium surface tension at CMC (γcmc), solubility, and Krafft temperature were measured, and the effect of structural modifications on surface active properties and micelle formation was discussed.

Physico-chemical properties and cytotoxic effects of sugar-based surfactants: Impact of structural variations.

Surfactants derived from the biorefinery process can present interesting surface-active properties, low cytotoxicity, high biocompatibility and biodegradability. They are therefore considered as potential sustainable substitutes to currently used petroleum-based surfactants. To better understand and anticipate their performances, structure-property relationships need to be carefully investigated. For this reason, we applied a multidisciplinary approach to systematically explore the effect of subtle structural variations on both physico-chemical properties and biological effects. Four sugar-based surfactants, each with an eight carbon alkyl chain bound to a glucose or maltose head group by an amide linkage, were synthesized and evaluated together along with two commercially available standard surfactants. Physico-chemical properties including solubility, Krafft point, surface-tension lowering and critical micellar concentration (CMC) in water and biological medium were explored. Cytotoxicity evaluation by measuring proliferation index and metabolic activity against dermal fibroblasts showed that all surfactants studied may induce cell death at low concentrations (below their CMC). Results revealed significant differences in both physico-chemical properties and cytotoxic effects depending on molecule structural features, such as the position of the linkage on the sugar head-group, or the orientation of the amide linkage. Furthermore, the cytotoxic response increased with the reduction of surfactant CMC. This study underscores the relevance of a methodical and multidisciplinary approach that enables the consideration of surfactant solution properties when applied to biological materials. Overall, our results will contribute to a better understanding of the concomitant impact of surfactant structure at physico-chemical and biological levels.

Mixed O/W emulsions stabilized by solid particles: a model system for controlled mass transfer triggered by surfactant addition.

This article deals with a model mixed oil-in-water (O/W) emulsion system developed to study the effect of surfactants on mass transfer between dispersed oil droplets of different composition. In this purpose, our goal was to formulate O/W emulsions without any surface active agents as stabilizer, which was achieved by replacing surfactants by a mixture of hydrophilic/hydrophobic silica particles. Then, to study the specific role of surfactants in the oil transfer process, different types and concentrations of surfactants were added to the mixed emulsion after its preparation. In such a way, the same original emulsion can be used for all experiments and the influence of various surface active molecules on the oil transfer mechanism can be directly studied. The model mixed emulsion used consists of a mixture of hexadecane-in-water and tetradecane-in-water emulsions. The transfer between tetradecane and hexadecane droplets was monitored by using differential scanning calorimetry, which allows the detection of freezing and melting signals characteristic of the composition of the dispersed oil droplets. The results obtained showed that it is possible to trigger the transfer of tetradecane towards hexadecane droplets by adding surfactants at concentrations above their critical micellar concentration, measured in presence of solid particles, through micellar transport mechanism.