Microalgae as Soft Permeable Particles.

The colloidal stability of non-motile algal cells in water drives their distribution in space. An accurate description of the interfacial properties of microalgae is therefore critical to understand how microalgae concentrations can change in their biotope or during harvesting processes. Here, we probe the surface charges of three unicellular algae─Chlorella vulgaris, Nannochloropsis oculata, and Tetraselmis suecica─through their electrophoretic mobility. Ohshima's soft particle theory describes the electrokinetic properties of particles covered by a permeable polyelectrolyte layer, a usual case for biological particles. The results appear to fit the predictions of Ohshima's theory, proving that all three microalgae behave electrokinetically as soft particles. This allowed us to estimate two characteristic parameters of the polyelectrolyte external layer of microalgae: the volume charge density and the hydrodynamic penetration length. Results were compared with transmission electron microscopy observations of the algal cells' surfaces, and in particular of their extracellular polymeric layer, which was identified with the permeable shell evidenced by electrophoretic measurements. Noticeably, the algal surface potentials estimated from electrophoretic mobility using the soft particle theory are less negative than the apparent zeta potentials. This finding indicates that electrostatics are expected to play a minor role in phenomena of environmental and industrial importance, such as microalgae aggregation or adhesion.

Straightforward Assessment of Wettability Changes by Washburn Capillary Rise: Toward a Screening Tool for Selecting Water Compositions for Improved Oil Recovery.

Evaluating the wettability state of reservoir rocks is key for understanding and optimizing waterflooding and improved oil recovery techniques that imply the use of low-salinity water. Aside from established petrophysical techniques, such as Amott imbibition tests, we evaluated the Washburn capillary rise method as a low-cost, easy-to-implement, and rapid screening tool for probing the wettability state of rock samples. The well-known limitations of this method are discussed and circumvented. We show that measuring the capillary rise of two liquids -brine and n-octane-is required to assess the evolution of the wettability state of a material induced by various treatments. The wettability state is quantified by the adhesion tension of brine to the solid. The higher the adhesion tension of brine, the more water-wet the sample. An increase in oil-wetness is observed when the sample is contacted with a crude oil or its released waters; an increase in water-wetness is obtained by postcontacting the oil-wet sample with low-salinity brine or surfactant solutions. The Washburn capillary rise is revealed to be a robust method for screening wettability alteration. With a typical duration of 1-10 min, it allows reproducibility check and screening of a wide range of brine compositions in a reasonable time frame. Therefore, it is a relevant tool to identify the most favorable brine compositions to be tested afterward with more time-consuming techniques, such as Amott tests and corefloods.

Exploring carbonate rock wettability across scales: Role of (bio)minerals.

HYPOTHESIS: The wettability of carbonate rocks is expected to be affected by the organic components of biominerals which are complex, nanostructured organo-mineral assemblages. Elucidating the nanoscale mechanisms driving the wettability of solid surfaces will enable a better understanding of the role of biominerals in the wetting properties of carbonate rocks to control various geological, environmental and industrial processes. EXPERIMENTS: Using Atomic Force Microscopy and Spectroscopy (AFM/AFS) we probed the wettability properties of carbonate rocks with different amounts of organic material. The adhesion properties of two types of limestones were determined in liquid environments at different length scales (nm to mm) using functionalized tips with different chemical groups to determine the extent of surface hydrophobic and hydrophilic organo-mineral interactions. FINDINGS: We observed homogeneous hydrophobic areas at length scales below < 5 µm. The origin of this hydrophobicity is linked to the presence of organics, whose amount and spatial distribution depend on the rock composition. Specifically, our results reveal that the biogenic vs non-biogenic origin of the mineral grains is the main rock property controlling the wettability of the solid surface. Overall, our methodology offers a multi-scale approach to unravel the role that organic moieties and biominerals play in controlling the wettability of rock-water interfaces.

Effect of chain unsaturation on the self-association of tri- and tetraethylene glycol octyl ethers obtained by butadiene telomerization.

2,7-Octadienyl ethers of tri- and tetraethylene glycol (C(8:2)E(3) and C(8:2)E(4)) have been synthesized by the atom-economical butadiene telomerization of the corresponding poly(ethylene glycols). On one hand, this synthetic path is attractive because it is expeditious and environmentally benign, and on the other hand, it provides unconventional amphiphiles for which the lipophilic chains possess two double bonds. These two unsaturations increase the global hydrophilicity of the compound, which is also highlighted by the modelization of the compounds using the conductor-like screening model for real solvents (COSMO-RS). The behavior of C(8:2)E(3) and C(8:2)E(4) in binary amphiphile/water and ternary amphiphile/oil/water systems is therefore greatly modified compared to that of the conventional fully saturated homologues (C(8)E(3) and C(8)E(4)) that are easily obtained after hydrogenation. This results in a lowered efficiency of the unsaturated compounds for oil solubilization. The usual Winsor-type microemulsion systems are formed, and for the same oil, the DLS investigation of the microstructure of the Winsor I microemulsion does not highlight any difference in the self-association between the unsaturated and saturated compounds.

The Salinity-Phase-Inversion method (SPI-slope): A straightforward experimental approach to assess the hydrophilic-lipophilic-ratio and the salt-sensitivity of surfactants.

HYPOTHESIS: The salinity at which the dynamic phase inversion of the reference system C10E4/n-Octane/Water occurs in the presence of increasing amounts of a test surfactant S2 provides quantitative information on the hydrophilic/lipophilic ratio and on the sensitivity to NaClaq of S2. EXPERIENCES: The Salinities causing the Phase Inversion (SPI) of the reference system mixed with 12 ionic and 10 nonionic well-defined surfactants are determined in order to quantify the contributions of the nature of the polar head and of the alkyl chain length. FINDINGS: The SPI varies linearly upon the addition of S2. The slope of the straight variation with the molar fraction of S2 is called the "SPI-slope". It quantifies the hydrophilic/lipophilic ratio of S2 in saline environment and its salt-sensitivity with respect to the reference surfactant C10E4. The SPI-slopes of C12 surfactants bearing different polar heads are found to decrease in the following order: C12NMe3Br > C12E8 > C12E7 ≥C12SO3Na ≈ C12COONa ≥ C12SO4Na > C12E6 > C12E5 > C12E3. This classification is different from that obtained when the phase inversion is caused by a change in temperature (PIT-slope method) because the addition of NaCl in significant amounts (3 to 10 wt%) partially screens the ionic heads and diminishes their apparent hydrophilicities. A simple model, valid for all types of nonionic surfactants, is developed on the basis of the HLDN equation (Normalized Hydrophilic-Lipophilic Deviation) to express the SPI-slope as a function of the hydrophilic/lipophilic ratio (PACN2) and the salinity coefficient (δ2) of S2. All studied surfactants are positioned on a 2D map according to the values of their SPI-slope and their PIT-slope to graphically highlight their hydrophilic/lipophilic ratio and their salt-sensitivity. Finally, a linear model connecting the PIT-slope and the SPI-slope is derived for nonionics, emphasizing that the thermal partitioning of C10E4 towards n-octane is much greater in the PIT-slope than in the SPI-slope experiments.

Classification of organic solvents revisited by using the COSMO-RS approach.

A new approach for the classification of solvents is proposed, based solely on the solvent molecular structure and relying on the "COnductor-like Screening MOdel for Real Solvents" (COSMO-RS), in which solvents are considered in their liquid state. This approach provides an a priori classification without requiring the knowledge of any experimental data. The theoretical descriptors of the proposed classification are generated through the analysis of the COSMO-RS σ-potential profiles. By applying a two-step statistical procedure to the descriptors generated for a set of 153 representative solvents, a clustering into 10 classes leads to an optimal classification that is compared to the classical Chastrette's classification. The investigation of nitrocellulose solubility allows a validation of the proposed classification, which can be extended also to solvent mixtures. This new approach for solvent classification, thus, appears as a consistent tool for the design of new solvents and their formulation.

Hexahydrofarnesyl as an original bio-sourced alkyl chain for the preparation of glycosides surfactants with enhanced physicochemical properties.

Five new bio-based surfactants have been synthetized by coupling hexahydrofarnesol with mono and di-saccharides. Hexahydrofarnesol (3,7,11-trimethyl-dodecan-1-ol) is a by-product of the industrial production of farnesane, a sustainable aviation fuel obtained by a fermentation process from sugar feedstocks. Using hexahydrofarnesol as the lipophilic starting material allows obtaining 100% bio-based surfactants while valorizing an industrial by-product. Moreover, the C15-branched alkyl chain brings unique properties to the surfactants. This paper presents a physicochemical characterization of these new surfactants including their behaviors in water (water solubility, critical micellar concentration and surface tension) and in oil/water systems (interfacial tension against model oil and ternary phase behavior). Their hydrophilicities have been determined thanks to the PIT-slope method and compared to the ones of standard surfactants with linear alkyl chains, in order to distinguish the contributions of the sugar polar heads and of the branched hexahydrofarnesyl lipophilic chain. This novel class of surfactants combines the properties of sugar-based surfactants (low sensitivity to temperature and salinity, ability to form Winsor III microemulsion systems over a wide range of salinity), along with specificities linked to the branched alkyl chain (lower Krafft temperature, low surface tension).

Amphiphilic properties of hydrotropes derived from isosorbide: endo/exo isomeric effects and temperature dependence.

The hydrotropic properties of short-chain monoalkyl ethers of isosorbide have been studied with emphasis on the difference between the two regioisomers (2-O- and 5-O-monoalkylisosorbide, C(i)Iso-exo and C(i)Iso-endo, respectively). On the one hand, the partitioning in a water/cyclohexane system has been measured, and on the other hand, the "optimal formulation" of C(i)Iso/oil/water systems has been determined by changing the oil polarity. In both cases, whatever the alkyl chain length (four or five carbons), C(i)Iso-exo appears to be less hydrophilic due to an intramolecular hydrogen bond that makes the free hydroxyl group less available. With one substituted position, the hydrophilicity contribution of isosorbide is slightly higher than the one of two ethylene glycols when the exo hydroxyl remains free, whereas it is closer to one ethylene glycol when this hydroxyl is substituted. With regard to the sensitivity to temperature, the hydrophilicity loss on heating seems to be similar for both isomers and close to what is obtained for poly(ethylene glycol) derivatives if we consider the evolution of the partition coefficients. In C(i)Iso-endo/oil/water systems, however, the variation of the optimal oil with temperature tends to show that the isosorbide derivatives are approximately 2 times less sensitive than their poly(ethylene glycol) counterparts to temperature changes.

Using the dynamic Phase Inversion Temperature (PIT) as a fast and effective method to track optimum formulation for Enhanced Oil Recovery.

HYPOTHESIS: The attainment of ultralow interfacial tensions between crude oil and injected aqueous surfactant mixtures is a prerequisite for an effective chemical Enhanced Oil Recovery (EOR). The dynamic Phase Inversion Temperature (PIT) of SOW emulsified systems is very close to the "optimum temperature" currently identified with equilibrated SOW systems. Therefore, the PIT could be a tool to track the "optimum formulation" and determine EACN of crude oils. Additionally, the PIT-slope method could be used to characterize EOR surfactants. EXPERIMENTS: The PIT of 3% C10E4/crude oils/water emulsions are compared to the PIT for n-alkanes in order to estimate crude oils EACN. The "PIT-slope" method is applied to different non-ionic and ionic extended EOR surfactants to assess their amphiphilicity. The conductivity profiles of different EOR surfactants/crude oil/NaCl(aq) emulsions at fw = 0.5 are determined at different salinities. FINDINGS: Considering the PIT shifts and shapes, it is possible to infer relevant information on the crude oil such as precise EACN and relationships between optimum salinity and temperature. The "PIT-Slope method" allows ranking EOR surfactants according to their amphiphilicity. Mixing both results allows a faster determination of key parameters used in EOR compared to studies with equilibrated system.

Synthesis and amphiphilic properties of decanoyl esters of tri- and tetraethylene glycol.

Well-defined decanoyl triethylene glycol ester and decanoyl tetraethylene glycol ester were synthesized and compared to their ether counterparts (C(10)E(4) and C(10)E(3)). Their physicochemical properties i.e. critical micelle concentrations (CMC), cloud points, and equilibrium surface tensions were determined. Binary water-surfactant phase behavior was also studied by polarized optical microscopy. The stability of the ester bond was determined by investigating alkaline hydrolysis of the compounds. It was found that CMC, cloud point and equilibrium surface tension are roughly the same for corresponding ethers and esters. In the binary diagram, the esters form only lamellar phases, the area of which is smaller than that of the ether counterparts. These different behaviors can be related to the modification of the molecular conformation induced by the replacement of the ether group by the ester group.

Synthesis, surfactant properties and antimicrobial activities of methyl glycopyranoside ethers.

A series of amphiphilic methyl glucopyranoside ethers incorporating various alkyl chain lengths has been synthesized from commercially available methyl glucopyranosides following an acetalisation/hydrogenolysis sequence. The amphiphilic properties of ethers and acetal intermediates were evaluated. Both families exhibit excellent surfactant properties with a maximum efficiency obtained for compounds bearing a linear dodecyl chain (CMC = 0.012 mM, γsat. = 30 mN m-1). Antimicrobial activity studies revealed an efficient activity (0.03 < MIC < 0.12 mM) against Gram-positive bacteria such as Listeria monocytogenes, Enterococcus faecalis, Enterococcus faecium and Staphylococcus aureus. More importantly, these compounds were found to be active against multi-resistant strains such as vancomycin-, methicillin- and daptomycin-resistant strains. Finally, it was found that antimicrobial activities are closely related to physicochemical properties and are also influenced by the nature of the carbohydrate moiety.

Concentration measurements of sucrose and sugar surfactants solutions by using the 1H NMR ERETIC method.

The ERETIC method has been used to determine precise concentrations of aqueous solutions of sucrose and sugar surfactants, namely octyl glucoside and fatty acid sucrose esters by (1)H NMR spectroscopy. The effects of NMR tuning, acquisition parameters, and spectrum processing on the measurement have been assessed in these particular cases. The linearity upholds over the whole concentration range, with both sucrose and octyl glucoside, whatever the physicochemical phenomena occurring, either an increasing viscosity or the micellization of the surfactant. For sucrose solutions, an accuracy of 2% is measured for concentrations between 0.1 and 200 mmol/L, which is consistent with literature data.

PFGSE-NMR study of the self-diffusion of sucrose fatty acid monoesters in water.

The micellization of pure monosubstituted sucrose fatty acid esters in water, namely sucrose octanoate, sucrose decanoate, sucrose laurate, sucrose dodec-5-cis-enoate, sucrose myristate, and sucrose palmitate, has been investigated by means of two NMR methods, pulsed field gradient spin-echo NMR (PFGSE-NMR), giving access to the self-diffusion coefficients of free molecules and micelles in solution, and the ERETIC method (electronic reference to access in vivo concentrations) for the measurement of concentrations by external calibration of a synthetic NMR signal. The early micellar regions and, when possible, the premicellar regions were investigated. By this method, we obtained the hydrodynamic radii of micelles, displaying a linear progression in relation to the chain length and an accurate determination of critical micellar concentration (CMC) for each sucrose ester. The effect of the regiochemistry of fatty chain grafting has been investigated, showing special behavior for 1'-O-sucrose palmitate.

Structure-interfacial properties relationship and quantification of the amphiphilicity of well-defined ionic and non-ionic surfactants using the PIT-slope method.

The Phase Inversion Temperature of a reference C10E4/n-Octane/Water system exhibits a quasi-linear variation versus the mole fraction of a second surfactant S2 added in the mixture. This variation was recently proposed as a classification tool to quantify the Hydrophilic-Lipophilic Balance (HLB) of commercial surfactants. The feasibility of the so-called PIT-slope method for a wide range of well-defined non-ionic and ionic surfactants is investigated. The comparison of various surfactants having the same dodecyl chain tail allows to rank the polar head hydrophilicity as: SO3Na⩾SO4Na⩾NMe3Br>E2SO3Na≈CO2Na⩾E1SO3Na⩾PhSO3Na>Isosorbide(exo)SO4Na≫IsosorbideendoSO4Na≫E8⩾NMe2O>E7>E6⩾Glucosyl>E5⩾Diglyceryl⩾E4>E3>E2≈Isosorbide(exo)>Glyceryl>Isosorbide(endo). The influence on the surfactant HLB of other structural parameters, i.e. hydrophobic chain length, unsaturation, replacement of Na(+) by K(+) counterion, and isomerism is also investigated. Finally, the method is successfully used to predict the optimal formulation of a new bio-based surfactant, 1-O-dodecyldiglycerol, when performing an oil scan at 25 °C.

A bilayer to monolayer phase transition in liquid crystal glycolipids.

Investigations of the thermotropic liquid-crystalline properties of 6,6'-di-O-stearoylsucrose show, for the first time, that glycolipids can exhibit phase transitions within the smectic A phase.

Hydrotropic properties of alkyl and aryl glycerol monoethers.

Three pentyl and three aryl 1-O-monoglyceryl ethers prepared via a green catalytic route were investigated as hydrotropic solvents. Their amphiphilicities were quantified by comparing their so-called "fish" diagrams constructed with oils of increasing hydrophobicity (EACN). For the same number of carbon atoms, the presence of a methyl substituent in ß position makes the hydrotrope slightly more hydrophobic, as evidenced by the more hydrophobic optimal oil. Branched isomers are also less efficient since they require higher concentrations to get microemulsions. The presence of an aromatic moiety within the hydrophobic chain increases the solubility of the hydrotrope in water in comparison to the alkyl derivative that has the same number of carbon atoms. It also modifies significantly the associative behavior in oil/water systems: Benzylglycerol monoether is able to form Winsor III systems, just as the pentyl derivatives, but with much more polar oils, whereas phenylglycerol is not. In oil/water systems, all glycerol-derived amphiphiles exhibit a twice-lower temperature-sensitivity compared to their ethyleneglycol counterparts. The pentyl and benzyl 1-O-monoglyceryl ethers can be classified as amphiphilic solvents, or "solvo-surfactants", as regards to their surface-active properties and good solubilizing abilities.

Classification of ester oils according to their Equivalent Alkane Carbon Number (EACN) and asymmetry of fish diagrams of C10E4/ester oil/water systems.

The phase behavior of well-defined C10E4/ester oil/water systems versus temperature was investigated. Fifteen ester oils were studied and their Equivalent Alkane Carbon Numbers (EACNs) were determined from the so-called fish-tail temperature T* of the fish diagrams obtained with an equal weight amount of oil and water (f(w)=0.5). The influence of the chemical structure of linear monoester on EACN was quantitatively rationalized in terms of ester bonds position and total carbon number, and explained by the influence of these polar oils on the "effective" packing parameter of the interfacial surfactant, which takes into account its entire physicochemical environment. In order to compare the behaviors of typical mono-, di-, and triester oils, three fish diagrams were entirely plotted with isopropyl myristate, bis (2-ethylhexyl) adipate, and glycerol trioctanoate. When the number of ester bonds increases, a more pronounced asymmetry of the three-phase body of the fish diagram with respect to T* is observed. In this case, T* is much closer to the upper limit temperature Tu than to the lower limit temperature Tl of the three-phase zone. This asymmetry is suggested to be linked to an increased solubility of the surfactant in the oil phase, which decreases the surfactant availability for the interfacial pseudo-phase. As a consequence, the asymmetry depends on the water-oil ratio, and a method is proposed to determine the fw value at which T* is located at the mean value of Tu and Tl.

Synthesis and foaming properties of new anionic surfactants based on a renewable building block: sodium dodecyl isosorbide sulfates.

Two agro-based anionic surfactants containing an isosorbide moiety have been synthesized and their amphiphilic properties evaluated. Since isosorbide is now considered as an important platform chemical of the starch industry, these compounds could represent bio-sourced alternatives to the alkyl ether sulfates (notably lauryl ether sulfate, LES) that are based on petroleum-derived ethylene oxides. As isosorbide is an asymmetric diol, two isomers can be prepared (2-O-dodecyl isosorbide sulfate and 5-O-dodecyl isosorbide sulfate) that show significantly different aqueous properties as regards to their Krafft temperatures and critical micellar concentrations. 5-O-dodecyl isosorbide sulfate is the most soluble and the most efficient surfactant. It possesses a much lower critical micelle concentration (cmc) than sodium dodecyl sulfate, SDS, leading to comparable foaming properties with a three times lower concentration. Its behavior compares well with the one of pure diethoxylated dodecyl sulfate that has also been prepared and evaluated in this work.

Telomerisation of 1,3-butadiene with 1,4:3,6-dianhydrohexitols: an atom-economic and selective synthesis of amphiphilic monoethers from agro-based diols.

The telomerisation of 1,3-butadiene with a Pd/TPPTS catalytic system in water or an organic solvent was used for the synthesis of C8 ethers from isosorbide, an agro-based diol. The use of water/oil biphasic reaction conditions allowed the selective synthesis of monoethers with improved rates upon using inorganic bases as promotors. As isosorbide is a non-symmetric diol, the two hydroxyl groups display different reactivities. 2-O-substituted-monoethers were preferentially obtained if water was used as the solvent, whereas in DMSO 5-O-substituted monoethers were the major products. Complete conversions of isosorbide with up to 94% monoether selectivities were obtained. The optimized reaction conditions were successfully applied to isomannide and isoidide for the selective synthesis of the derived ethers. An improved reactivity of the endo-hydroxy groups of isosorbide and isomannide versus the exo-hydroxy groups of isosorbide and isoidide was observed if the reaction was performed in DMSO instead of water.

Bidimensional analysis of the phase behavior of a well-defined surfactant (C10E4)/oil (n-octane)/water-temperature system.

The equilibrium phase behavior of the well-defined system tetraethyleneglycol decyl ether (C(10)E(4))/n-octane/water (SOW) at variable temperature (T) was revisited by careful analysis of the three bidimensional cuts, namely, the gamma (at constant water-oil ratio), chi (at constant surfactant concentration), and Delta (at constant temperature) plots. A straightforward methodology is reported to determine the frontiers of the triphasic (Winsor III) domain on any cut of the SOW-T phase prism. It comes from the systematic analysis of another cut, here gamma at different water-oil ratios and chi at different surfactant concentrations from the knowledge of Delta cuts at different temperatures. The method has been validated through comparison with experimental results. It enables one to show, for the first time, the evolution of a SOW system three-phase body contours with (i) water-oil ratio, (ii) surfactant concentration, and (iii) temperature. It exhibits a strong impact of the surfactant affinity for the pure oil and water phases on the shape of the phase diagrams. The systematic study of the effect of the surfactant concentration on the aspect of the chi plot sheds light on an unusual shape found at low surfactant concentration.