Toroidal micelles formed in viscoelastic aqueous solutions of a double-tailed surfactant with two quaternary ammonium head groups.

Innovation in surfactant structures is an effective way to prepare new soft materials with novel applications. In this study, we synthesized a double-tailed surfactant containing two quaternary ammonium head groups (Di-C12-N2). The Di-C12-N2 solution behavior was investigated by surface tension, fluorescence, rheology, and cryo-TEM methods. Although Di-C12-N2 contained a large double-tailed hydrophobic group, the solubility of Di-C12-N2 was ∼90 mmol L-1 at 25 °C with a Krafft temperature of ∼1 °C. The increase in Di-C12-N2 concentration in the solutions led to the formation of various aggregates, including spherical micelles, worm-like micelles, multi-layered vesicles, and a rare type of small toroidal micelles. The two quaternary ammonium head groups in Di-C12-N2 led to strong electrostatic interactions between molecules, which was critical for the formation of toroidal micelles. Moreover, with an added NaCl concentration of 40 mmol L-1, the viscosity of the 5 mmol L-1Di-C12-N2 solution increased by ∼1000 times compared to the pure 5 mmol L-1Di-C12-N2 solution, revealing the high sensitivity of the unique head groups to ionic strength. This study enriches the research on the self-assembly principles of surfactants and brings new potential applications for new soft materials.

Wormlike micellar solutions formed by an anionic surfactant and a cationic surfactant with two head groups.

Innovation in the molecular structure of surfactants is important for the preparation of soft materials with novel properties. In this study, we synthesized a cationic surfactant, N1,N1,N1,N1,N3,N3,N3-pentamethyl-N3-(3-stearamidopropyl)propane-1,3-diammonium bromide, hereafter referred to as C18-DQA. Unlike conventional cationic surfactants, C18-DQA contains two quaternary ammonium head groups and a long-saturated alkyl chain equal to a chain length of 21 carbon atoms. C18-DQA exhibits a low Krafft point of ∼0 °C and a water solubility >1000 mM at 25 °C. The critical micelle concentration (cmc) of C18-DQA was determined to be 0.59 mM using the Nile red method. C18-DQA was mixed with sodium laurate (SL) at different molar ratios to produce transparent solutions with excellent viscoelasticity over a wide concentration range. The 1 : 1.5 molar ratio C18-DQA/SL mixed solutions exhibited gel-like behavior for a total surfactant concentration of 2.88 wt% (75 mM). The solution with a total surfactant concentration of 300 mM (120 mM C18-DQA and 180 mM SL) achieved a maximum zero-shear viscosity (η0) of 4224 Pa s. Cryogenic transmission electron microscopy analysis revealed the formation of extremely long wormlike micelles, with a cross-sectional diameter of 5 nm and contour length >3 µm, in the mixed solutions. C18-DQA and SL molecules were drawn close by electrostatic attractions, leading to a suitable molecular geometry for the extensive growth of wormlike micelles. This work will act as an important reference for the future preparation of highly viscoelastic solutions by mixing cationic and anionic surfactants. The proposed system is also expected to have potential applications in cosmetic formulations, home care products, and oilfield fracturing fluids.

Smart Emulsions Stabilized by a Multi-headgroup Surfactant Tolerant to High Concentrations of Acids and Salts.

Retaining emulsions stable at high acidity and salinity is still a great challenge. Here, we report a novel multi-headgroup surfactant (C3 H7 -NH+ (C10 COOH)2 , di-UAPAc) which can be reversibly transformed among cationic, anionic and zwitterionic forms upon pH variation. Stable oil-in-dispersion (OID) emulsions in strong acidity (pH=2) can be co-stabilized by low concentrations of di-UAPAc and silica nanoparticles. High salinity at pH=2 improves the adsorption of di-UAPAc on silica particles through hydrogen bonding, resulting in the transformation of OID emulsions into Pickering emulsions. Moreover, emulsification/demulsification and interconversion between OID and Pickering emulsions together with control of the viscosity and droplet size can be triggered by pH. The present work provides a new protocol for designing surfactants for various applications in harsh aqueous media, such as strong acidity and high salinity, involved in oil recovery and sewerage treatments.

Ecofriendly Viscoelastic Solutions Formed from a Recyclable Rosin-Based Amine Oxide Surfactant.

Innovations in molecular structures formed using bioresources are efficient means to prepare surfactant aggregates with unique properties. Here, a rosin-based amine oxide surfactant (R-11-3-AO) containing large hydrophobic groups was synthesized from rosin derivatives, namely, dehydroabietic acid and long-chain amino acids. Cryo-transmission electron microscopy showed that R-11-3-AO molecules formed extremely long wormlike micelles with a cross-sectional diameter of 4-5 nm at a concentration of approximately 7 mmol·L-1. A gel-like system was obtained at approximately 30 mmol·L-1 due to the dense entanglement of the wormlike micelles. The solutions also exhibited unique shear thickening behavior at a shear rate of approximately 10 s-1 even at high concentrations. The large hydrophobic group contained in R-11-3-AO is the origin of the strong van der Waals interactions between the surfactant molecules, resulting in the rapid growth of wormlike micelles. This rosin-based surfactant is the first recoverable amine oxide surfactant from solutions through the salting-out effect with high recovery rates. This work demonstrates the unique capabilities of rosin-based surfactants for forming wormlike micelles and provides opportunities for the development of surfactant recovery technologies.

Recyclable Nonionic-Anionic Bola Surfactant as a Stabilizer of Size-Controllable and pH-Responsive Pickering Emulsions.

A novel nonionic-anionic Bola surfactant (abbreviated as CH3O(EO)7-R11-COOH) was designed and synthesized by condensation of methyl polyoxyethylene (7) ether with 12-bromododecanoic acid. In neutral aqueous solution, the surfactant behaves as a nonionic one and can stabilize oil-in-water (O/W) conventional emulsions alone and costabilize O/W Pickering emulsions with positively charged alumina nanoparticles with n-decane as the oil. In alkaline solution, the carboxylic acid group is deprotonated, becoming anionic and the surfactant is converted to Bola form, which is an inferior emulsifier and does not adsorb on particle surfaces, resulting in demulsification of both kinds of emulsions. With strong hydrophilicity, both the Bola surfactant and the bare particles return to the aqueous phase after demulsification, which is therefore recyclable and reusable in accordance with sustainable chemistry and engineering. In acidic media between pH 3 and 6, the ethyleneoxy groups tend to desorb from particle surfaces, slightly reducing the hydrophobicity of the particles. However, Pickering emulsions are still stable but their droplet size increases on lowering the pH. The Pickering emulsions are therefore pH-responsive and size-controllable. This newly designed Bola surfactant is effective in preparing smart emulsions, which are extensively applied in heterogeneous catalysis, oil product transportation, emulsion polymerization, and new material preparation.

Charge Density Overcomes Steric Hindrance of Ferrocene Surfactant in Switchable Oil-in-Dispersion Emulsions.

A ferrocene surfactant can be switched between single and double head form (FcN+ C12 /Fc+ N+ C12 ) triggered by redox reaction. FcN+ C12 can neither stabilize an O/W emulsion alone nor an oil-in-dispersion emulsion in combination with alumina nanoparticles due to the steric hindrance of the ferrocene group. However, such steric hindrance can be overcome by increasing the charge density in Fc+ N+ C12 , so that oil-in-dispersion emulsions can be co-stabilized by Fc+ N+ C12 and alumina nanoparticles at very low concentrations (1×10-7  M (≈50 ppb) and 0.001 wt %, respectively). Not only can reversible formation/destabilization of oil-in-dispersion emulsions be achieved by redox reaction, but also reversible transformation between oil-in-dispersion emulsions and Pickering emulsions can be obtained through reversing the charge of alumina particles by adjusting the pH. The results provide a new protocol for the design of surfactants for stabilization of smart oil-in-dispersion emulsions.

Pickering Emulsions Synergistically Stabilized by Aliphatic Primary Amines and Silica Nanoparticles.

Innovation in emulsion compositions is necessary to enrich emulsion formulations and applications. Herein, Pickering emulsions were prepared using silica nanoparticles and aliphatic primary amines with an oil-water ratio of 1:1 (v/v). Contact angle experiments revealed that the in situ hydrophobization of nanoparticles was caused by the surface adsorption of amine molecules. Notably, the interactions between amine compounds and the surface of silica nanoparticles were electrostatic attractions and mutual hydrogen bonding. The existence of hydrogen bonds was further confirmed by demulsification experiments using a chaotropic agent DMF and increasing temperatures. The hydrophobicity of silica nanoparticles can be effectively improved using most commercially available aliphatic primary amines such as n-hexylamine, n-octylamine, n-decylamine, dodecylamine, and tetradecylamine. The minimum concentrations of the aforementioned amines necessary for stabilizing the emulsions with 0.3 wt % silica nanoparticles are 3, 0.6, 0.3, 0.06, and 0.03 mM, respectively, decreasing significantly with increasing alkyl chain length. With the increase of the amine concentrations, the hydrophobicity of silica particles monotonically increased and finally resulted in the inversion of emulsions. The amine concentrations for emulsion phase inversion were 150, 40, 30, 20, and 20 mM, respectively, in the presence of 0.3 wt % silica nanoparticles. In this work, silica nanoparticles were hydrophobized using aliphatic primary amines. The composite stabilizers developed are useful for developing novel stimuli-responsive Pickering emulsions, while the synergistic effects introduced herein are also helpful in expanding the hydrophobization methods available for nanoparticles.

Multiple Pickering emulsions stabilized by the same particles with different extent of hydrophobization in situ.

Multiple emulsions are widely used in pharmaceuticals, foods, and cosmetics. However, those stabilized by surfactants with different HLB values are generally unstable due to the diffusion of the surfactants between inner and outer interfaces. Here, we report that multiple W/O/W emulsions can be prepared by using the same particles in combination with a surfactant of different concentrations. The less surface-active raw CaCO3 nanoparticles can be hydrophobized to surface-active in situ by adsorption of the anionic surfactant SDS, and the wettability of the particles can be controlled to be suitable for stabilizing both O/W and W/O Pickering emulsions by adjusting the surfactant concentration. With toluene as oil phase, the CaCO3 particles at 1.0 wt% tend to stabilize a W/O emulsion in the presence of 3 mm SDS in an aqueous solution, which can then be further dispersed in an aqueous phase with 1.0 wt% CaCO3 and SDS below 1 mm to form a W/O/W multiple emulsion. The effects of the ratio of W/O emulsion to the outer water phase and the preparation methods on stabilization of multiple emulsions were examined. With a ratio smaller than 3:1 and by gentle magnetic stirring, the multiple emulsions obtained can stay stable for at least a month without coalescence. This simple method not only ensures stabilization of multiple emulsions but also avoids complicated synthesis of colloid particles with different wettability.

Rheological behavior of thread-like fiber solutions formed from a rosin-based surfactant with two head groups.

Wormlike micelles are conventional aggregates that exist in viscoelastic solutions. However, to achieve a solution with prominent viscoelasticity, rather high concentrations of surfactants are usually required due to the flexibility of aggregates in solution. If thread-like aggregates with rigidity can be formed by surfactants, the solutions are expected to show strong viscoelasticity at very low surfactant concentrations. Herein, A novel rosin-based quaternary ammonium surfactant with two head groups (abbreviated as R-11-3-DA) was synthesized. Cryogenic transmission electron microscopy (Cryo-TEM) images showed that flexible nanofibers with diameters of about 7-8 nm and lengths of over 1 µm were formed in the 1 : 1.5 R-11-3-DA : SL solutions. The rigidity of the aggregates seems to be inherited from the rigidity of the surfactant molecules. The novel aggregates endow the solutions with remarkable viscoelasticity at very low concentrations, with a critical overlap concentration of 0.01 wt% and a critical gelling concentration of 0.58 wt%. The rheological behavior of the solutions also shows excellent shear resistance and weak sensitivity to temperature below the critical gelation temperature (Tgel). This work reveals the advantages of viscoelastic solutions containing flexible nanofibers. The design principles of new molecular structures and system compositions can be applied to the preparation of smart soft materials based on the self-assembly of molecules.

Oil-in-Water emulsions stabilized by alumina nanoparticles with organic electrolytes: Fate of particles.

HYPOTHESIS: Oil-in-dispersion emulsions can be stabilized by like charged particles and surfactant. Surfactant adsorbs at the oil-water interface to reduce the interfacial tension and endow the interface with charge, while particles remain dispersed in the aqueous phase to provide electrostatic repulsion between droplets and particles. Can weakly surface-active organic electrolytes adsorb at the oil-water interface and behave like surfactants in stabilizing oil-in-dispersion emulsions with like charged particles? EXPERIMENTS: Symmetrical organic electrolytes, tetraalkylammonium bromides (R4NBr), with either no or very low interfacial activity endowing oil droplets with charge were combined with alumina nanoparticles to stabilize emulsions. The effect of R chain length (varying from methyl to butyl) on the type and stability of emulsions was investigated. FINDINGS: Mixtures of high concentrations of short chain R4NBr salts (R = methyl or ethyl) and alumina particles stabilise oil-in-water Pickering emulsions, whereas longer chain (R = propyl or butyl) analogues stabilize oil-in-dispersion emulsions assisted by alumina particles. Tetrapropylammonium and tetrabutylammonium cations adsorb at the oil-water interface reducing the interfacial tension and endowing the interface with charge. The stability of the oil-in-dispersion emulsions is dominated by the electrostatic repulsion between the droplets and between droplets and particles in the continuous aqueous phase.

Water-in-Oil Emulsion Gels Stabilized by a Low-Molecular Weight Organogelator Derived from Dehydroabietic Acid.

High concentrations of surfactants or gelators are usually necessary to prepare emulsions gels with unusual physicochemical properties. This situation may be improved by innovating the aggregate morphology in systems. Herein, a rosin-based molecule is designed and synthesized using dehydroabietic acid as the starting material (denoted as R-Lys-R). The molecule acts as an effective organogelator and can gelate several hydrocarbon compounds with a minimum gelation concentration of 0.2% (w/v). Analysis using atomic force microscopy (AFM) and circular dichroism (CD) reveals that in n-decane, R-Lys-R forms left-handed helical fibers with a cross-sectional diameter of approximately 15 nm. The directional hydrogen bonding of the amide group is helpful to the formation of aggregates. At concentrations of R-Lys-R above 2%, water-in-oil emulsions are transformed into emulsion gels owing to the aptitude of R-Lys-R in gelating the oil phase. The concentrations of the emulsifier can be adjusted to obtain emulsion gels with different formulations. This work reveals the potential of rosin derivatives for the formation of small molecular weight organogels and provides a novel method for the utilization of natural resources in soft materials and home care products.

Recyclable and re-usable smart surfactant for stabilization of various multi-responsive emulsions alone or with nanoparticles.

A novel multi-responsive surfactant (abbreviated as N+-8P8-N) was synthesized, in which one octyl trimethylamine group (quaternary ammonium) and one octyl dimethylamine group are connected to a benzene ring through ether bonds. This novel surfactant can stabilize conventional oil-in-water (O/W) emulsions alone, and O/W Pickering emulsions and novel oil-in-dispersion emulsions together with oppositely and similarly charged nanoparticles, respectively. In all cases rapid demulsification can be achieved through either pH or CO2/N2 triggers, by which the surfactant is reversibly converted between a normal cationic surfactant form (N+-8P8-N) and a strongly hydrophilic and surface-inactive bola form (N+-8P8-NH+). Notably, the bola form N+-8P8-NH+ dissolves in the aqueous phase alone or together with nanoparticles after demulsification without contamination of the oil phase, and the aqueous phase can be recycled many times triggered by pH or CO2/N2 in accordance with the principle of green chemistry. This newly designed re-usable smart surfactant is significant for the development of various temporarily stable emulsions, which are extensively applied in emulsion polymerization, new material synthesis, heterogeneous catalysis and oil transportation.

Conversion of bile salts from inferior emulsifier to efficient smart emulsifier assisted by negatively charged nanoparticles at low concentrations.

Bile salts (BS), one of the biological amphiphiles, are usually used as solubilizing/emulsifying agents of lipids or drugs. However, BS such as sodium deoxycholate (NaDC) can't stabilize an oil-in-water (O/W) emulsion alone due to its unusual molecular structure. In this paper we report that these emulsifiers with poor emulsifying ability can be transformed to highly efficient emulsifiers by combining with negatively charged particles (silica or montmorillonite). Both together can synergistically co-stabilize oil-in-water emulsions at extremely low concentrations (minimum 0.01 mM NaDC plus 0.003 wt% particles). Moreover, the emulsions can be reversibly switched between stable and unstable triggered by CO2/N2 at room temperature. This strategy is universal for emulsions containing different oils (alkanes, aromatic hydrocarbons and triglycerides) and for different BS and offers a generic model for a variety of BS of different molecular structure, which will extend their applications in more technical fields such as emulsion polymerization, biphasic catalysis and emulsion extraction.

Formation of asymmetric belt-like aggregates from a bio-based surfactant derived from dehydroabietic acid.

The morphology and physicochemical properties of ordered molecular aggregates are closely related to surfactant molecules. Herein, a rosin-based amine oxide surfactant containing a large hydrophobic group (abbreviated R-10-AO) was synthesized from dehydroabietic acid, which is an important derivative of rosin. Cryogenic transmission electron microscopy (cryo-TEM) images and small-angle X-ray scattering (SAXS) showed that at a concentration of ∼5 mM, R-10-AO molecules formed flexible nanobelts with a thickness of only 2-3 nm. The width of these nanobelts was 50-150 nm and the length was more than 1 µm. The formation of the stable nanobelts arose from the strong van der Waals forces of the bulky hydrophobic portions of R-10-AO in solution, facilitating the stability of the asymmetrical aggregates. Rheological tests showed that the formed nanobelts were thermodynamically stable. The entanglement of these nanobelts led to significant viscoelasticity of the solutions. The zero-shear viscosity (η0) of the R-10-AO solution reached 10 Pa s at a concentration of 5 mM, which is much greater than that of most wormlike micellar solutions. This work provides the inspirations of preparing aggregates with novel properties using natural products.

pH-Responsive Behavior of Pickering Emulsions Stabilized by a Selenium-Containing Surfactant and Alumina Nanoparticles.

Herein, we describe pH-responsive Pickering emulsions stabilized by a sodium carboxylate-derived selenium surfactant (C10-Se-C10·(COONa)2) in combination with positively charged alumina nanoparticles. Unlike other bola-type carboxylate surfactants (e.g., disodium eicosanoate), C10-Se-C10·(COONa)2 is soluble in water with a low Krafft temperature (36.1 °C). The emulsions are sensitive to pH variations, and efficient demulsification can be achieved by a pH trigger. The carboxylic sodium group in the C10-Se-C10·(COONa)2 structure can be reversibly cycled between its anionic and nonionic states (carboxylic acid), resulting in a pH-controlled electrostatic attraction between the surfactant and alumina. The Pickering emulsion can be reversibly switched between "on" (stable) and "off" (unstable) states by pH at least four times. Compared with the emulsions stabilized by specially synthesized stimuli-responsive particles or surfactants, the method reported here is much easier to implement and requires very low concentrations of the surfactant and nanoparticles, with potential applications in the fields of biomedicine, drug delivery, and cosmetics.

Charge-Reversible Surfactant-Induced Transformation Between Oil-in-Dispersion Emulsions and Pickering Emulsions.

A novel charge-reversible surfactant, (CH3 )2 N-(CH2 )10 COONa, was designed and synthesized, which together with silica nanoparticles can stabilize a smart n-octane-in-water emulsion responsive to pH. At high pH (9.3) the surfactant is anionic carboxylate, which together with the negatively charged silica nanoparticles co-stabilize flowable oil-in-dispersion emulsions, whereas at low pH (4.1) it is turned to cationic form by forming amine salt which can hydrophobize in situ the negatively charged silica nanoparticles to stabilize viscous oil-in-water (O/W) Pickering emulsions. At neutral pH (7.5), however, this surfactant is converted to zwitterionic form, which only weakly hydrophobises the silica particles to stabilize O/W Pickering emulsions of large droplet size. Moreover, demulsification can be achieved rapidly triggered by pH. With this strategy particles can be controlled either dispersed in water or adsorbed at the oil-water interface endowing emulsions with the capacity for intelligent and precise control of stability as well as viscosity and droplet size.

Behavior of Smart Surfactants in Stabilizing pH-Responsive Emulsions.

Newly structured pH-responsive smart surfactants (N+ -(n)-N, n=14, 16) from alkyl trimethylammonium bromides are reported. In neutral and alkaline media N+ -(n)-N behaves as a normal cationic surfactant and stabilizes conventional emulsions alone, as well as Pickering emulsions and oil-in-dispersion emulsions together with oppositely and similarly charged nanoparticles, respectively. In acidic media N+ -(n)-N becomes a hydrophilic Bola-type surfactant, N+ -(n)-NH+ , and is an inferior emulsifier either when used alone or together with charged nanoparticles, resulting in demulsification. N+ -(n)-NH+ returns to the aqueous phase alone or together with nanoparticles after demulsification without contaminating the oil phase, and the aqueous phase can be recycled when triggered by pH change. This protocol is a green process and leads to preparation of various temporarily stable emulsions which are often used in emulsion polymerization, heterogeneous catalysis, and oil transportation.

Transition between a Pickering Emulsion and an Oil-in-Dispersion Emulsion Costabilized by Alumina Nanoparticles and a Cationic Surfactant.

The transition between a novel oil-in-dispersion emulsion and an oil-in-water (O/W) Pickering emulsion triggered by pH was achieved using alumina nanoparticles in combination with a cationic surfactant. In acidic and neutral aqueous media, positively charged particles and the surfactant both at very low concentrations costabilize an oil-in-dispersion emulsion with the surfactant adsorbed at droplet interfaces and particles dispersed in the aqueous phase between the droplets. In alkaline media, however, particles become negatively charged and are hydrophobized in situ by adsorption of the surfactant to become surface-active and stabilize an O/W Pickering emulsion. The transition between the two is also possible by lowering the pH. The transformation can be achieved several times in a mixture of 0.1 wt % nanoparticles and 0.01 mM surfactant. This transition is significant, since particles can be made to either adsorb at the oil-water interface, which is beneficial for applications like biphasic catalysis, or remain dispersed in the aqueous phase, which is favorable for their recovery and reuse.

Redox-Responsive Oil-In-Dispersion Emulsions Stabilized by Similarly Charged Ferrocene Surfactants and Alumina Nanoparticles.

A redox-responsive oil-in-dispersion emulsion was developed by using a cationic ferrocene surfactant (FcCOC10N) and Al2O3 nanoparticles, in which the required concentrations of FcCOC10N and Al2O3 nanoparticles are as low as 0.001 mM (≈0.005 cmc) and 0.006 wt %, respectively. Rapid demulsification can be successfully achieved through a redox trigger, resulting from the transition of FcCOC10N from a normal cationic surfactant form into a strongly hydrophilic Bola type form (Fc+COC10N). Moreover, Fc+COC10N together with the particles almost resides in the aqueous phase and can be recovered after the reduction reaction. Not only the amount of surfactant and nanoparticles are significantly reduced but also the emulsifier (surfactant and alumina) can be recycled and reused from the aqueous phase, which is a sustainable and economical strategy for various applications.

Stimuli-Responsive Biomass Cellulose Particles Being Able to Reversibly Self-Assemble at Fluid Interface.

Stimuli-responsive surface-active microcrystalline cellulose (MCC) particles are obtained by interaction with conventional cationic surfactants such as cetyltrimethylammonium bromide (CTAB) in aqueous media, where MCC are in situ hydrophobized by adsorption of the cationic surfactant in water via electrostatic interaction and with the in situ hydrophobization removed by adding an equimolar amount of an anionic surfactant such as sodium dodecyl sulfate (SDS). The trigger is that the electrostatic interaction between the oppositely charged ionic surfactants is stronger than that between the cationic surfactant and the negative charges on particle surfaces, or the anionic surfactant prefers to form ion pairs with the cationic surfactants and thus making them desorbed from surface of MCC. Reversible O/W Pickering emulsions can then be obtained by using the MCC in combination with trace amount of a cationic surfactant and an anionic surfactant, and the anionic surfactant with a longer alkyl chain is more efficient for demulsification. With excellent biocompatibility, biodegradability, and renewability, as well as low toxicity, the biomass cellulose particles that can be made stimuli-responsive and able to reversibly self-assemble at fluid interface become ideal biocompatible particulate materials with extensive applications involving emulsions and foams.