Surfactant Polar Head Research Articles

Unveiling the formation capacity of multicomponent oleogels: Performance of lecithin interacting with monostearate derivatives

Oleogels have been explored as fat substitutes due to their healthier composition compared to trans and saturated fats, also presenting interesting technological perspectives. The aim of this study was to investigate the compositional perspective of multicomponent oleogels. Structuring ability of lecithin (LEC) (20 or 90 wt% of phosphatidylcholine – PC) combined with glycerol monostearate (GMS), sorbitan monostearate (SMS) or sucrose monostearate (SAC) in sunflower oil was evaluated from oleogels properties. The thermal and rheological properties, microstructure and stability of the oleogels were affected by the difference in the chemical composition of LEC and the ratio between LEC and different surfactants. Interestingly, low-phosphatidylcholine LEC (L20) performed better, although systems formed with reduced amounts of LEC tended to be softer (LEC-GMS) and present high oil holding capacity (LEC-SMS). The mixtures of LEC and monostearate-based surfactants showed different behaviors, depending on the surfactant polar head. In LEC-GMS systems, LEC hindered the self-assembly of GMS in sunflower oil, compromising mechanical properties and increasing oil release. When combined with SMS, LEC acted as a crystal habit modifier of SMS, forming a more homogeneous microstructure and producing stronger oleogels with greater oil binding capacity. However, above the threshold concentration, LEC prevented SMS self-assembly, resulting in a weaker gel. A positive interaction was found in LEC-SAC formulations in specific ratios, since SAC cannot act as a single oleogelator. Results show the impact of solubility balance played by LEC and fatty-acid derivatives surfactant when combined and used as oleogelators. This knowledge can contribute to a rational perspective in the preparation and modulation of the properties of edible oleogels.

Symmetry (Asymmetry) of the Molar Excess Gibbs Free Energy Function of the Binary Mixed Micelles of Bile Acid Anion and Classical Cationic Surfactant: Influence of Sterically Shielded and Sterically Unshielded Polar Groups of the Steroid Skeleton

Binary mixtures of surfactants build a binary mixed micelle in which the ratio of surfactants usually differs from the initial ratio of surfactants in their binary mixture. The thermodynamic stabilization of the binary mixed micellar pseudophase about the hypothetical ideal state (intermolecular interactions between the different particles and the conformational states of the particles are identical to those of monocomponent states) is described by the molar excess Gibbs free energy (gE). The dependence of gE on the molar fraction of surfactant i (xi) from the binary mixed micelle can be described by a symmetric function (symmetry is described to the line parallel to the y-axis and passes through xi = 0.5) or by an asymmetric function. Theoretical analysis (canonical partition function, conformational analysis) examines how the presence of different polar functional groups, some of which are sterically shielded from the steroid skeleton of bile salts (surfactant), affect the symmetry of the function gE of the binary mixed micelle of the cholic acid anion (bile salts) and classic cationic surfactant (hydrophobic tail and polar head). Suppose the steroid skeleton of the bile salt contains non-sterically shielded polar groups (or the temperature is relatively high). In that case, gE is a symmetric function. At the same time, if the steroid skeleton also contains sterically shielded polar groups, then the gE function is asymmetric.

Emulsification of low viscosity oil in alkali-activated materials

This research aims to understand the mechanisms enhancing the fixation of low viscosity mineral oils, including tailings, in reactive inorganic matrices, by emulsification. To this purpose, significant amounts of a model low viscosity pure mineral oil (20%vol) are immobilized in alkali-activated materials (AAM), either based on metakaolin or blast furnace slag. In such case, Portland cement-based matrices are not adequate (emulsification delicate to manage and excessive setting retardation). Various surfactants are used to ease the oil emulsion.Visual observation and rheology evidence two distinct groups of surfactants. One contributes to structuring the oil/AAM fresh mix, with greater viscosity than without surfactant; the other includes non-structuring surfactants, without change in viscosity. Each group depends on the AAM considered.Whatever the AAM and the surfactant, the oil droplet size decreases significantly, without consistent correlation with the interfacial tension between oil/activating solution (AS). Interfacial tension alone does not explain the reduction in oil droplet size. Characterization of diluted ternary suspensions (solid particles – oil – AS) relates the structuring effect to interactions between oil and solid particles, through the surfactant polar head groups and non-polar hydrocarbon tails. A detailed mechanism explaining the oil stabilization and the mix structuring is discussed.

Concentrated phases of an ionic surfactant (Aerosol OT) in polar solvents

AbstractWe have studied concentrated phases of Aerosol OT (AOT) in polar (water, ethylene glycol, formamide, N,N‐dimethylformamide) and apolar (isooctane) solvents. We investigated two surfactant volume fractions (φ = 0.2 and φ = 0.6) with small angle x‐ray scattering (SAXS), rheology and electrical conductivity experiments. AOT self‐assembles differently depending on solvent type and concentration. SAXS experiments show that the AOT/water system displays a lamellar phase. In the other cases, only formamide displays a lamellar phase for φ = 0.6. The other solvents (and formamide at φ = 0.2) promote the self‐assembly of AOT in other microstructures. The SAXS spectra display correlation peaks consistent with a disordered array of cylindrical aggregates. The microstructure of the AOT/isooctane system at φ = 0.2 is that of an arrangement of spherical aggregates. The results are explained in terms of surfactant packing models and solvent properties. For instance, the ability of ethylene glycol to form hydrogen bonds with AOT promotes the formation of cylindrical aggregates by increasing the area per surfactant polar head. As N,N‐dimethylformamide is slightly miscible in hydrocarbons it increases the volume of the surfactant tail promoting reverse structures.

Influence of surfactant's polar head group charge on the self-assembly of three PEO–PPO–PEO triblock copolymers of widely varying hydrophobicity

The present study is based on the interaction between three polyethylene oxide-polypropylene oxide-polyethylene oxide (PEO-PPO-PEO) triblock copolymers namely Pluronics® L81, P84 and F88 (with same PPO Mol. Wt. but 10,40 and 80% PEO, respectively) and the ionic surfactants with 12-C chain but different polar head group charge viz. sodium dodecyl sulfate (SDS, anionic), dodecyl trimethylammonium bromide (DTAB, cationic) and N-dodecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (C12PS, zwitterionic) using plethora of techniques. The most hydrophobic Pluronic® L81 (cloud point, CP = 16.5 °C (5%w/w)) remains as molecularly dissolved below the CP and forms unstable vesicles close to CP, moderately hydrophobic, P84 (CP = 73.6 °C), remains molecularly dissolved below 15 °C and forms core-shell micelle above critical micelle temperature (CMT) and the highly hydrophilic F88 forms micelles at elevated temperatures. Micellization and dye solubilizing ability improved in the presence of salt (sodium chloride, NaCl). The presence of ionic surfactants leads to small sized surfactant rich micelles with progressive addition as confirmed by dynamic light scattering (DLS) and small angle neutron scattering (SANS). Amongst the three copolymers, P84 (Nagg ≈ 72) showed maximum solubility of dye and lowering power of CMC (CAC < 2 mM), hence SANS studies were limited to P84 and it was observed that SDS (Nagg ≈ 45) showed stronger interactions with P84 as compared to DTAB (Nagg ≈ 53) and C12PS (Nagg ≈ 83).

The significant effects of linear medium chain fatty alcohols on phase behavior of aqueous solution of mixed cationic–anionic surfactant

The effect of 1-hexanol on the phase behavior of aqueous solutions of sodium dodecyl sulfate (SDS) and cetyl trimethyl ammonium bromide (CTAB) has been systematically studied. The phase ranges of vesicle and liquid crystal (LC) can be greatly extended with the addition of 1-hexanol. These specific structures distributed symmetrically on the two sides of the SDS/CTAB equimolar line in the pseudo ternary phase diagram. The aqueous two phase system (ATPS) contained vesicles that would transform into lamellar LC with the change of ratio of SDS/CTAB. The phase behaviors of SDS/CTAB system with addition of different alcohols (C5OH–C8OH) showed similar trends in structural transition except for phase span, demonstrating that the obstruction of electrostatic interaction between surfactant polar heads was affected by the insertion depth of the added alcohols.

Effective osmotic cohesion due to the solvent molecules in a delocalized adsorbed monolayer

A molecular thermodynamic model is derived for an uncharged delocalized surfactant monolayer adsorbed at a liquid interface, taking explicit account for the solvent molecules present in the monolayer. The model is based on the scaled particle theory of hard-disc mixtures, and is also extended to sticky discs (i.e. attraction between the adsorbed molecules). Upon compression of the adsorbed layer, the solvent is expelled from it. The respective osmotic effect on the equation of state is shown to be equivalent to an effective lateral depletion attraction between the surfactant molecules. This effective osmotic cohesion causes an increase of the value of the attraction parameter β of the monolayer. The smaller the size of the surfactant polar head group is, the larger the effective attraction the model predicts. This trend is verified with data for the adsorption at water|air surface of alcohols, undissociated acids, and hexaethylenglycol monoalkyl ethers. The proposed theory allows the amount of solvent in the monolayer to be estimated, which is shown to be important for the neutron reflectivity of the surface.

Selective extraction of lipase and amylase from enzyme mixture by employing liquid emulsion membrane.

This work deals with the extraction of lipase and amylase from enzyme mixture by employing liquid emulsion membranes (LEM). The electrostatic interaction between enzymes and reverse micellar surfactant polar head group plays an important role for selective extraction of two different enzymes having different isoelectric points. The optimized conditions for lipase extraction (pH 7.0) resulted in the purification fold and activity recovery of 5.43 fold and 89.53%, respectively, whereas, in case of amylase (pH 9.0) the purification fold and activity recovery were 6.58 and 94.32%, respectively. The results were compared with the control sample (containing individual enzymes) and mixture of enzymes lipase and amylase and it was shown that for optimum conditions the activity recovery and purification fold was higher for the individual enzymes as compared to their mixture. Downstream processing involving LEM was shown to be a feasible method for selective extraction of enzymes. © 2018 American Institute of Chemical Engineers Biotechnol. Prog., 34:721-729, 2018.

Nanoscale Control Over Interfacial Properties in Mixed Reverse Micelles Formulated by Using Sodium 1,4‐bis‐2‐ethylhexylsulfosuccinate and Tri‐n‐octyl Phosphine Oxide Surfactants

The interfacial properties of pure reverse micelles (RMs) are a consequence of the magnitude and nature of noncovalent interactions between confined water and the surfactant polar head. Addition of a second surfactant to form mixed RMs is expected to influence these interactions and thus affect these properties at the nanoscale level. Herein, pure and mixed RMs stabilized by sodium 1,4-bis-2-ethylhexylsulfosuccinate and tri-n-octyl phosphine oxide (TOPO) surfactants in n-heptane were formulated and studied by varying both the water content and the TOPO mole fraction. The microenvironment generated was sensed by following the solvatochromic behavior of the 1-methyl-8-oxyquinolinium betaine probe and (31) P NMR spectroscopy. The results reveal unique properties of mixed RMs and we give experimental evidence that free water can be detected in the polar core of the mixed RMs at very low water content. We anticipate that these findings will have an impact on the use of such media as nanoreactors for many types of chemical reactions, such as enzymatic reactions and nanoparticle synthesis.

Formulation, high throughput in vitro screening and in vivo functional characterization of nanoemulsion-based intranasal vaccine adjuvants.

Vaccine adjuvants have been reported to induce both mucosal and systemic immunity when applied to mucosal surfaces and this dual response appears important for protection against certain pathogens. Despite the potential advantages, however, no mucosal adjuvants are currently approved for human use. Evaluating compounds as mucosal adjuvants is a slow and costly process due to the need for lengthy animal immunogenicity studies. We have constructed a library of 112 intranasal adjuvant candidate formulations consisting of oil-in-water nanoemulsions that contain various cationic and nonionic surfactants. To facilitate adjuvant development we first evaluated this library in a series of high-throughput, in vitro assays for activities associated with innate and adaptive immune activation in vivo. These in vitro assays screened for the ability of the adjuvant to bind to mucin, induce cytotoxicity, facilitate antigen uptake in epithelial and dendritic cells, and activate cellular pathways. We then sought to determine how these parameters related to adjuvant activity in vivo. While the in vitro assays alone were not enough to predict the in vivo adjuvant activity completely, several interesting relationships were found with immune responses in mice. Furthermore, by varying the physicochemical properties of the surfactant components (charge, surfactant polar head size and hydrophobicity) and the surfactant blend ratio of the formulations, the strength and type of the immune response generated (TH1, TH2, TH17) could be modulated. These findings suggest the possibility of using high-throughput screens to aid in the design of custom adjuvants with unique immunological profiles to match specific mucosal vaccine applications.

Ionic liquids entrapped in reverse micelles as nanoreactors for bimolecular nucleophilic substitution reaction. Effect of the confinement on the chloride ion availability.

In this work was explored how the confinement of two ionic liquids (ILs), 1-butyl-3-methylimidazolium chloride (bmimCl) and 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF4), inside toluene/benzyl-n-hexadecyldimethylammonium chloride (BHDC) reverse micelles (RMs) affects the Cl(-) nucleophilicity on the bimolecular nucleophilic substitution (SN2) reaction between this anion and dimethyl-4-nitrophenylsulfonium trifluoromethanesulfonate. The results obtained show that, upon confinement, the ionic interactions between the ILs with the cationic surfactant polar head group and the surfactant counterion modify substantially the performance of both ILs as solvents. In toluene/BHDC/bmimCl RMs, the Cl(-) interacts strongly with bmim(+) (and/or BHD(+)) in such a way that its nucleophilicity is reduced in comparison with neat IL. In toluene/BHDC/bmimBF4 RMs, an ionic exchange equilibrium produces segregation of bmim(+) and BF4(-) ions, changing the composition of the RMs interface and affecting dramatically the Cl(-) availability. These results show the versatility of this kind of organized system to alter the ionic organization and influence on reaction rate when used as nanoreactors.

Structure, stability, and fragmentation of sodium bis(2-ethylhexyl)sulfosuccinate negatively charged aggregates in vacuo by MD simulations.

Negatively charged supramolecular aggregates formed in vacuo by n bis(2-ethylhexyl)sulfosuccinate (AOT(-)) anions and n + n(c) sodium counterions (i.e., [AOT(n) Na(n+nc)](nc)) have been investigated by molecular dynamics (MD) simulations for n = 1 to 20 and n(c) = -1 to -5. By comparing the maximum excess charge values of negatively and positively charged AOTNa aggregates, it is found that the charge storage capability is higher for the latter systems, the difference decreasing as the aggregation number increases. Statistical analysis of physical properties like gyration radii and moment of inertia tensors of aggregates provides detailed information on their structural properties. Even for n(c) = -5, all stable aggregates show a reverse micelle-like structure with an internal core, including sodium counterions and surfactant polar heads, surrounded by an external layer consisting of the surfactant alkyl chains. Interestingly, the reverse micelle-like structure is retained also in proximity of fragmentation. Moreover, the aggregate shapes may be approximated by elongated ellipsoids whose longer axis increases with n and |n(c)|. The fragmentation patterns of a number of these aggregates have also been examined and have been found to markedly depend on the aggregate charge state. The simulated fragmentation patterns of a representative aggregate show good agreement with experimental data obtained using low collision voltages.

Supramolecular Assemblies Obtained by Mixing Different Cyclodextrins and AOT or BHDC Reverse Micelles

In this contribution we show the effect of the surfactant polar head and the external solvent on the incorporation of different cyclodextrins (CDs) {α-CD, β-CD, γ-CD, decenylsuccinyl-β-CD (Mod-β-CD), and hydroxypropyl-β-CD (hp-β-CD)} in different reverse micelles (RMs) {benzene/sodium 1,4-bis(2-ethylhexyl) sulfosuccinate(AOT)/water, and benzene/benzyl-n-hexadecyldimethylammonium chloride (BHDC)/water} and compare them with previous results obtained in n-heptane/AOT/water RMs. To investigate the different systems, we have used UV-vis spectrophotometry, induced circular dichroism spectroscopy (ICD), and the achiral molecular probe methyl orange (MO). The results show dramatic differences changing the external solvent and the surfactant, which are explained by considering the differences in the RMs interface composition, the water-surfactant interaction, and the CDs' location in the different media investigated. None of the CDs were incorporated into the benzene/AOT/water RMs at any [H2O]/[surfactant] ratio studied (W0) whereas it was previously shown that Mod-β-CD and hp-β-CD could be included in n-heptane/AOT/water RMs. However, all of the CDs are incorporated in benzene/BHDC/water RMs at W0> 10 and hp-β-CD is dissolved even at W0 = 0. Different from what was found in n-heptane/AOT RMs, in BHDC RMs MO showed ICD signals with two different CDs: Mod-β-CD and hp-β-CD. The results are explained by considering the known difference in the interfacial water structure for AOT and BHDC RMs and the electron-rich region on the secondary hydroxyl (wider side of the CDs), which helps to solubilize all CDs in BHDC. This study shows that chiral cyclodextrin could be available for a guest in an organic medium such as the RMs. Therefore we have created a potentially powerful nanoreactor with two different confined regions in the same aggregate: the polar core of the RMs and the chiral hydrophobic cavity of cyclodextrin.

Paramagnetic Relaxation Enhancement Experiments: A Valuable Tool for the Characterization of Micellar Nanodevices

Micellar incorporation of hydrophobic molecular receptors is a promising strategy to obtain efficient nanodevices that work in water. In order to fully evaluate the potential of this approach, information on the localization and orientation of the receptor inside the micelle are necessary. Systematic studies undertaken on a uranyl-salophen receptor incorporated into CTABr and CTACl micelles show that nuclear magnetic resonance paramagnetic relaxation enhancement (NMR-PRE) experiments are particularly suitable to provide this type of information. The effect on the measurements of surfactant concentration, nature of the surfactant polar head, and ionic strength is also reported. Notably the normalization procedure applied to the obtained data can be considered of general application, thus enabling the comparison of information collected for different types of supramolecular micelle/receptor systems.

Effects of surfactant concentration on alkyl chain arrangements in dry and swollen organic montmorillonite

To investigate the effects of surfactant concentration on alkyl chain arrangements in dry and swollen organic montmorillonite (OMt), Na+-montmorillonite (Na+-Mt) was modified with cationic surfactants with different alkyl chain lengths, including tetradecyl-trimethylammonium bromide (TTAB), cetyltrimethylammonium bromide (CTAB) and steartrimonium bromide (STAB), at a series of concentrations. The properties of dry and swollen OMt were characterized by thermal analysis and X-ray diffraction. Two kinds of novel arrangement of alkyl chains were found for dry CTAB-Mt. The surfactant polar head showed two arrangements when the CTAB concentration increased from 0.23 to 0.45 cation exchange capacity (CEC). The arrangement of the paraffin-type bilayer had a larger tilting angle at 1.93 CEC than that of reported research, leading to a maximum d-spacing of 5.81nm. For swollen CTAB-Mt in the solvent, the d-spacing first increased and then remained constant with increase in the amount of added CTAB. The swelling behavior was proposed, including three distinct stages: solvent-controlling stage, surfactant concentration-controlling stage, and alkyl chain length-controlling stage. The alkyl chain arrangements of dry and swollen OMt were further confirmed by TTAB-Mt and STAB-Mt.

Gas phase charged aggregates of bis(2-ethylhexyl)sulfosuccinate (AOT) and divalent metal ions: first evidence of AOT solvated aggregates

Assembling and chelating properties of sodium bis(2-ethylhexyl)sulfosuccinate (AOTNa) towards divalent metal ions have been investigated in the gas phase by electrospray ionization mass spectrometry. A variety of positively charged monometallated and mixed metal aggregates are formed. Interestingly, several ions contain solvent (MeOH, H(2)O) molecules and constitute the most abundant AOT cationic aggregates not containing sodium. These species are the first example of solvated AOT-metal ion aggregates in the gas phase. By increasing the surfactant aggregation number, the abundance of solvated species becomes lower than that of unsolvated ones. Decompositions of ionic species have been studied by tandem mass spectrometry, and their stability has been determined through energy resolved mass spectrometry. In contrast with positively charged AOT-alkaline metal ion aggregates, whose decompositions are dominated by the loss of individual surfactant molecules, AOTNa-divalent ion aggregates mainly dissociate through the cleavage of the AOT H(2)C-O bond followed by further intramolecular fragmentations. This finding, that is consistent with an enhanced chelation of divalent ions with AOT(-) head groups, has been taken as an indication that such aggregates are characterized by a reverse micelle-like organization with a ionic core formed by the metal cations interacting with the negatively charged surfactant polar heads, whereas the surfactant alkyl chains point outside.

A molecular dynamics study of structure, stability and fragmentation patterns of sodium bis(2-ethylhexyl)sulfosuccinate positively charged aggregates in vacuo

Positively charged supramolecular aggregates formed in vacuo by n AOTNa (sodium bis(2-ethylhexyl)sulfosuccinate) molecules and n(c) additional sodium ions, i.e. [AOT(n)Na(n+n(c))](n(c)), have been investigated by molecular dynamics (MD) simulations for n = 1-20 and n(c) = 0-5. Statistical analysis of physical quantities like gyration radii, atomic B-factors and moment of inertia tensors provides detailed information on their structural and dynamical properties. Even for n(c) = 5, all stable aggregates show a reverse micelle-like structure with an internal solid-like core including sodium counterions and surfactant polar heads surrounded by an external layer consisting of the surfactant alkyl chains. Moreover, the aggregate shapes may be approximated by rather flat and elongated ellipsoids whose longer axis increases with n and n(c). The fragmentation patterns of a number of these aggregates have also been examined and have been found to markedly depend on the aggregate charge state. In one particular case, for which experimental findings are available in the literature, a good agreement is found with the present fragmentation data.

New ammonium surfactant-stabilized rhodium(0) colloidal suspensions: Influence of novel counter-anions on physico-chemical and catalytic properties

Novel anionic species, such as hydrogen carbonate (HCO(3)(−)), fluoride (F(−)), triflate (CF(3)SO(3)(−)), tetrafluoroborate (BF(4)(−)) and chloride (Cl(−)) were investigated as new partners of water soluble N,N-dimethyl-N-cetyl-N-(2-hydroxyethyl) ammonium salts, used as a protective agent of rhodium colloids. The effect of the surfactant polar head on the micellar behavior, size and morphology of the nanospecies was studied by adapted physico-chemical experiments (surface tension measurements, dynamic light scattering, thermogravimetric and TEM analyses) and discussed in terms of strong or weak stabilization of the growing nanoparticles surface. Finally, the influence of the nanoenvironment generated by the surfactant with various counter-anions was evaluated via the hydrogenation of aromatics.

Understanding the Properties of the Coagel and Gel Phases: A 2H and 13C NMR Study of Amphiphilic Ascorbic Acid Derivatives

The coagel and gel phases formed by the d and l diastereoisomers of ascorbyl-dodecanoate (ASC12) in deuterated water were studied through solid-state NMR techniques. In particular, the dynamic properties of water and surfactant chains were investigated by (2)H and (13)C NMR static spectra, respectively. Two fractions of water with very different dynamics were found in the coagel phases, one solidlike and one liquidlike, assigned to water strongly bound to the surfactant polar heads and bulk water, respectively. Only one kind of "intermediate" water was instead detected in the gel phase suggesting that the merging of the two types of water in the interlayers between the surfactant lamellae occurs at the coagel-to-gel transition. Moreover, the surfactant chains, very rigid in the coagel phase, give rise to fast trans-gauche interconformational jumps in the gel phase, where almost isotropic reorientations of the whole aggregates also occur. A different dynamic behavior was found for the two diastereoisomers in particular for what concerns the surfactant molecules in the gel phase and the water molecules in the coagel presumably ascribable to different inter- and intramolecular interactions that involve the polar heads.

Rheological studies in the bulk and at the interface of Pickering oil/water emulsions

The rheological behavior and interfacial properties of olive oil–water emulsions stabilized by surfactant and clay particles (smectite) were studied to evaluate the effect of particles and surfactant distribution both in the bulk phase and at the oil–water interface. The temperature sweep of surfactant solutions and emulsions with and without clay particles showed the critical effect of the solid particles on the viscosity change. The mechanism of adsorption of surfactant molecules onto clay particles has a direct impact on the micellization and gelling temperatures. Indeed, the presence of clay particles caused a slight decrease in the micellization temperature and a total cancellation of the gelling phenomenon. Dynamic interfacial tension values demonstrated that clay particles would not compete with the surfactant for adsorption at the interface. However, the significant increase in the elastic properties of the interface that was observed accounts for their accumulation in the vicinity of the interface, probably at the level of surfactant polar head groups. Thus, the clay particles would form a mechanical barrier, preventing coalescence of emulsion droplets.