Pickering emulsions responsive to CO₂/N₂ and light dual stimuli at ambient temperature

A dual stimulus-responsive n-octane-in-water Pickering emulsion with CO₂/N₂ and light triggers is prepared using negatively charged silica nanoparticles in combination with a trace amount of dual switchable surfactant, 4-butyl-4-(4-N,N-dimethylbutoxyamine) azobenzene bicarbonate (AZO-B₄) as stabilizers. On one hand, the emulsion can be transformed between stable and unstable at ambient temperature rapidly via the N₂/CO₂ trigger, and on the other hand a change in droplet size of the emulsion can occur upon light irradiation/re-homogenization cycles without changing the particle/surfactant concentration. The dual responsiveness thus allows for a precise control of emulsion properties. Compared with emulsions stabilised by specially synthesized stimuli-responsive particles or by stimuli-responsive surfactants, the method reported here is much easier and requires relatively low concentration of surfactant (≈1/10 cmc), which is important for potential applications

Smart worm-like micelles responsive to CO₂/N₂ and light dual stimuli

CO₂/N₂ and light dual stimuli-reponsive worm-like micelles (WLMs) were obtained by addition of a relatively small amount of a switchable surfactant, 4-butyl-4´-(4-N,N-dimethylhexyloxy-amine) azobenzene bicarbonate (AZO-B6-CO₂), sensitive to the same triggers into a binary aqueous solution of cetyltrimethyl ammonium bromide (CTAB) and sodium salycilate (NaSal)

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 (C3H7−NH+(C10COOH)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

pH-responsive Pickering emulsions stabilized by silica nanoparticles in combination with a conventional zwitterionic surfactant

pH-responsive oil-in-water Pickering emulsions were prepared simply by using negatively charged silica nanoparticles in combination with a trace amount of a zwitterionic carboxyl betaine surfactant as stabilizer. Emulsions are stable to coalescence at pH 5 but phase separate completely at pH > 8.5. In acidic solution, the carboxyl betaine molecules become cationic allowing them to adsorb on silica nanoparticles via electrostatic interactions, thus hydrophobizing and flocculating them enhancing their surface activity. Upon increasing the pH, surfactant molecules are converted to witterionic form and significantly desorb from particles surfaces triggering de-hydrophobization and coalescence of oil droplets within the emulsion. The pH-responsive emulsion can be cycled between stable and unstable many times upon alternating the pH of the aqueous phase. The average droplet size in re-stabilized emulsions at low pH however increases gradually after four cycles due to the accumulation of NaCl. Experimental evidence including adsorption isotherms, zeta potentials, microscopy and three-phase contact angles is given to support the postulated mechanisms

Responsive aqueous foams stabilized by silica nanoparticles hydrophobized in situ with a conventional surfactant

In the recent past, switchable surfactants and switchable/stimulus-responsive surface-active particles have been of great interest. Both can be transformed between surface-active and surface-inactive states via several triggers, making them recoverable and reusable afterward. However, the synthesis of these materials is complicated. In this paper we report a facile protocol to obtain responsive surface-active nanoparticles and their use in preparing responsive particle-stabilized foams. Hydrophilic silica nanoparticles are initially hydrophobized in situ with a trace amount of a conventional cationic surfactant in water, rendering them surface-active such that they stabilize aqueous foams. The latter can then be destabilized by adding equal moles of an anionic surfactant, and restabilized by adding another trace amount of the cationic surfactant followed by shaking. The stabilization–destabilization of the foams can be cycled many times at room temperature. The trigger is the stronger electrostatic interaction between the oppositely charged surfactants than that between the cationic surfactant and the negatively charged particles. The added anionic surfactant tends to form ion pairs with the cationic surfactant, leading to desorption of the latter from particle surfaces and dehydrophobization of the particles. Upon addition of another trace amount of cationic surfactant, the particles are rehydrophobized in situ and can then stabilize foams again. This principle makes it possible to obtain responsive surface-active particles using commercially available inorganic nanoparticles and conventional surfactants

CO₂/N₂ triggered switchable Pickering emulsions stabilized by alumina nanoparticles in combination with a conventional anionic surfactant

Stable n-decane-in-water Pickering emulsions were prepared using positively charged alumina nanoparticles in combination with a trace amount of the anionic surfactant sodium dodecyl sulfate (SDS) as stabilizer. Particles were hydrophobized in situ by adsorption of surfactant enhancing their surface activity. Emulsions can be readily demulsified by addition of an equal amount of a switchable surfactant, N'-dodecyl-N,N-dimethylacetamidine (DDAA), which can be transformed between a surface-active amidinium/cationic form and a surface-inactive amidine/neutral form by bubbling CO₂ or N₂, respectively. Following addition of cationic DDAA which prefers to form ion pairs with SDS, desorption of SDS from particles surfaces occurs and alumina particles are rendered hydrophilic resulting in demulsification of the emulsion. However, by bubbling N₂ into the demulsified mixture, DDAA molecules are converted to the amidine/neutral form leading to collapse of the ion pairs and re-establishment of the in situ hydrophobization of particles. Stable Pickering emulsions can be prepared again following homogenization. This simple demulsification/re-stabilization cycle can be repeated several times. Experimental evidence including measurement of the adsorption isotherm, zeta potentials, extent of particle adsorption at droplets interfaces in emulsions and microscopy is given to support the postulated mechanisms

Biphasic biocatalysis using a CO2-switchable Pickering emulsion

Biphasic biocatalyses such as the hydrolysis of olive oil and the esterification of octanol with oleic acid were performed in a CO2/N2-switchable Pickering oil-in-water emulsion stabilized by silica nanoparticles hydrophobized in situ by a CO2/N2-switchable surfactant (N,N-dimethyldodecylamine). Compared with biphasic systems, the enzyme in the Pickering emulsions displays a higher reaction efficiency, and demulsification and recycling of the enzyme can be simply realized by bubbling with N2/CO2. Moreover, the recycled enzyme still possesses significant catalytic activity

Thermoresponsive Pickering emulsions stabilized by silica nanoparticles in combination with alkyl polyoxyethylene ether nonionic surfactant

We put forward a simple protocol to prepare thermo-responsive Pickering emulsions. Using hydrophilic silica nanoparticles in combination with a low concentration of alkyl polyoxyethylene monododecyl ether (C12En) nonionic surfactant as emulsifier, oil-in-water (o/w) emulsions can be obtained which are stable at room temperature but demulsified at elevated temperature. The stabilization can be restored once the separated mixture is cooled and re-homogenized, and this stabilization-destabilization behavior can be cycled many times. It is found that the adsorption of nonionic surfactant at the silica nanoparticle-water interface via hydrogen bonding between the oxygen atoms in the polyoxyethylene headgroup and the SiOH groups on particle surfaces at low temperature is responsible for the in situ hydrophobization of the particles rendering them surface-active. De-hydrophobization can be achieved at elevated temperature due to weakening or loss of this hydrogen bonding. The time required for demulsification decreases with increasing temperature and the temperature interval between stabilization and destabilization of the emulsions is affected by the surfactant headgroup length. Experimental evidence including microscopy, adsorption isotherms and three-phase contact angles is provided to support the mechanism

Widely adaptable oil-in-water gel emulsions stabilized by an amphiphilic hydrogelator derived from dehydroabietic acid

A surfactant, R-6-AO, derived from dehydroabietic acid has been synthesized. It behaves as a highly efficient low-molecular-weight hydrogelator with an extremely low critical gelation concentration (CGC) of 0.18 wt % (4 mm). R-6-AO not only stabilizes oil-in-water (O/W) emulsions at concentrations above its critical micelle concentration (cmc) of 0.6 mm, but also forms gel emulsions at concentrations beyond the CGC with the oil volume fraction freely adjustable between 2 % and 95 %. Cryo-TEM images reveal that R-6-AO molecules self-assemble into left-handed helical fibers with cross-sectional diameters of about 10 nm in pure water, which can be turned to very stable hydrogels at concentrations above the CGC. The gel emulsions stabilized by R-6-AO can be prepared with different oils (n-dodecane, n-decane, n-octane, soybean oil, olive oil, tricaprylin) owing to the tricyclic diterpene hydrophobic structure in their molecules that enables them to adopt a unique arrangement in the fibers

Edible oil-in-water emulsions stabilized by hydrophile–lipophile balanced sucrose ester

Conventional emulsions are mostly stabilized by surfactants and for stabilization of oil-in-water emulsions the surfactants should be hydrophilic or with HLB numbers larger than seven. In this work, we report that edible oil-in-water emulsions can also be stabilized by surfactants with an HLB value close to seven. With edible sucrose ester C-1807 (HLB no. = 7) as emulsifier and three edible oils (canola oil, olive oil, soybean oil), edible oil-in-water emulsions can be stabilized by C-1807 at concentrations beyond its critical aggregation concentration (CAC). Although monomeric C-1807 behaves as an inferior emulsifier, they assemble to form multilamellar vesicles in water at concentrations higher than the CAC giving a viscoelastic/gel-like aqueous phase which is partly responsible for emulsion stabilization. Specifically, at 2 wt%, high internal phase emulsions (HIPEs) with ϕo = 0.75 can be obtained, which are stable against cooling–heating cycles between 5 and 30°C during storage. The vesicles disperse in the aqueous lamellae surrounding the oil droplets, which together with the viscoelastic/gel-like continuous phase prevents them from flocculation and coalescence