Non-covalent reconfigurable microgel colloidosomes with a well-defined bilayer shell

Microgels are extremely interfacially active and are widely used to stabilize emulsions. However, they are commonly used to stabilize oil-in-water emulsions due to their intrinsic hydrophilicity and initially dispersed in water. In addition, there have been no attempts to control microgel structural layers that are formed at the interface and as a result it limits applications of microgel in advanced materials. Here, we show that by introducing octanol into poly(N-isopropylacrylamide-co-methacrylic acid) (PNIPAM-co-MAA) microgels, octanol-swollen microgels can rapidly diffuse from the initially dispersed oil phase onto the water droplet surface. This facilitates the formation of microgel-laden interfacial layers with strong elastic responses and also generates stable inverse water-in-oil Pickering emulsions. These emulsions can be used as templates to produce microgel colloidosomes, herein termed ‘microgelsomes’, with shells that can be fine-tuned from a particle monolayer to a well-defined bilayer. The microgelsomes can then be used to encapsulate and/or anchor nanoparticles, proteins, vitamin C, bio-based nanocrystals or enzymes. Moreover, the programmed release of these substances can be achieved by using ethanol as a trigger to mediate shell permeability. Thus, these reconfigurable microgelsomes with a microgel-bilayer shell can respond to external stimuli and demonstrate tailored properties, which offers novel insights into microgels and promise wider application of Pickering emulsions stabilized by soft colloids.

Inverse W/O Pickering emulsions and reconfigurable microgelsomes with a well-defined bilayer structure are prepared from octanol-swollen PNIPAM-co-MAA microgels and the combination of binary microgels, which promise wider application of soft colloids.     

Quantification of unadsorbed protein and surfactant emulsifiers in oil-in-water emulsions

Unadsorbed emulsifiers affect the physical and chemical behaviour of oil-in-water (O/W) emulsions. A simple methodology to quantify unadsorbed emulsifiers in the aqueous phase of O/W emulsions has been developed. Emulsions were centrifuged and filtered to separate the aqueous phase from the oil droplets and the concentration of unadsorbed emulsifiers in the aqueous phase determined. The quantification of unadsorbed surfactants based on the direct transesterification of their fatty acids was validated for Tween 20, Tween 80, citric acid ester (Citrem), Span 20 and monolauroyl glycerol. To determine unadsorbed proteins, results obtained with Folin-Ciocalteu reagent or UV-spectrophotometry were compared on emulsions stabilized by β-lactoglobulin (BLG), β-casein (BCN) or bovine serum albumin (BSA). The first method gave more accurate results especially during aging of emulsions in oxidative conditions. The whole methodology was applied to emulsions stabilized with single or mixed emulsifiers. This approach enables optimization of emulsion formulations and could be useful to follow changes in the levels of unadsorbed emulsifiers during physical or chemical aging processes.     

Initial inter-phase transport of compounds in a model emulsion system

Three-phase geranyl acetate emulsions stabilized by a non-ionic surfactant, Laureth 4, were prepared with a constant weight fraction of a lamellar liquid crystal and varied aqueous to oil phase weight ratios according to the phase diagram. The appearance and micrographs of the drop pattern versus time were recorded. As expected, emulsions with the lower values of the water to oil (W/O) ratio appeared to be of the W/O variety while the two more stable emulsions with the highest W/O ratio appeared as oil to water (O/W). Considering the surfactant exclusive solubility in the oil, this result was unexpected and the emulsions were investigated as to their structure. Unpredictably, all the emulsions were of the O/W kind; including the highest ratio of oil to water. The reason for this unanticipated outcome was the lamellar liquid crystal being dispersed into the aqueous phase at the slightest perturbation.     

Stability versus phase ratios of geranyl acetate three-phase emulsions

Three-phase geranyl acetate emulsions stabilized by a non-ionic surfactant, Laureth 4, were prepared with a constant weight fraction of a lamellar liquid crystal and varied aqueous to oil phase weight ratios according to the phase diagram. The appearance and micrographs of the drop pattern versus time were recorded. As expected, emulsions with the lower values of the water to oil (W/O) ratio appeared to be of the W/O variety while the two more stable emulsions with the highest W/O ratio appeared as oil to water (O/W). Considering the surfactant exclusive solubility in the oil, this result was unexpected and the emulsions were investigated as to their structure. Unpredictably, all the emulsions were of the O/W kind; including the highest ratio of oil to water. The reason for this unanticipated outcome was the lamellar liquid crystal being dispersed into the aqueous phase at the slightest perturbation.     

Effect of lateral heterogeneity in mixed surfactant-stabilized interfaces on the oxidation of unsaturated lipids in oil-in-water emulsions

The development of lipid oxidation in oil-in-water (O/W) emulsions is widely influenced by the properties of the interfacial layer, which separates the oil and water phases. In this work, the effect of the structure of the interface on the oxidative stability of surfactant stabilized O/W emulsions was investigated. Emulsions were prepared with either single Tween 20 or Tween 20/co-surfactant mixtures in limiting amounts. The co-surfactants, Span 20 and monolauroyl glycerol have the same hydrophobic tail as Tween 20 but differ by the size and composition of their polar headgroup. Metal-initiated lipid oxidation, monitored through the measurement of oxygen uptake, formation of conjugated dienes and volatile compounds, developed more rapidly in the emulsions stabilized by the surfactant mixture than in the single Tween 20-stabilized emulsion. The reconstitution of Tween 20/co-surfactant films at the air-water interface and their surface-pressure isotherms highlighted that, contrary to single Tween 20 molecules, Tween 20/co-surfactant mixtures exhibited an heterogeneous distribution within the interfacial layer, offering probably easier access of water-soluble pro-oxidants to the oil phase. These observations provide direct information about the link between the homogeneity of the interface layer and the oxidative stability of emulsions.     

Influence of Polyglycerol Polyricinoleate and Biopolymers on Physical Properties and Encapsulation Efficiency of Water-in-Oil-in-Water Emulsions Containing Mango Seed Kernel Extract

The influence of polyglycerol polyricinoleate (PGPR) and biopolymers (gelatin and sodium alginate) on the stabilization of water-in-oil (W/O) emulsions was investigated to improve the encapsulation efficiency (EE) of water-in-oil-in-water (W/O/W) emulsions containing mango seed kernel extract (MSKE). The physical properties and EE of the emulsions were found to depend more strongly on PGPR than on biopolymers. High EE values of MSKE were obtained when W/O emulsions stabilized by 4–8 wt% PGPR were incorporated with 1–5 wt% gelatin, or by 6–8 wt% PGPR incorporated with 0.5–1.5 wt% sodium alginate in the inner aqueous phase.     

纳米SiO2与阳离子表面活性剂的相互作用及其诱导的正辛烷-水乳状液的双重相转变

研究了3种不同结构的水溶性阳离子表面活性剂对纳米二氧化硅颗粒的原位表面活性化作用, 它们分别是单头单尾的十六烷基三甲基溴化铵(CTAB)、单头双尾的双十二烷基二甲基溴化铵(di-C12DMAB)和双头双尾的Gemini型阳离子三亚甲基-二(十四酰氧乙基溴化铵)(II-14-3), 并通过测定Zeta电位、吸附等温线及接触角等参数对相关机理进行了阐述. 结果表明, 阳离子表面活性剂吸附到颗粒/水界面形成以疏水基朝向水的单分子层, 从而增强了颗粒表面的疏水性是原位表面活性化的基础. 通过吸附CTAB和II-14-3, 颗粒的疏水性适当增强, 能吸附到正辛烷/水界面稳定O/W(1)型乳状液; 而通过吸附di-C12DMAB所形成的单分子层更加致密, 颗粒的疏水性进一步增强, 进而使乳状液从O/W(1)型转变为W/O型; 当表面活性剂浓度较高时, 由于链-链相互作用, 表面活性剂分子将在颗粒/水界面形成双层吸附, 使颗粒表面变得亲水而失去活性, 但此时体系中游离表面活性剂的浓度已增加到足以单独稳定O/W(2)型乳状液的程度. 因此当采用纳米二氧化硅和di-C12DMAB的混合物作乳化剂时, 通过增加di-C12DMAB的浓度即可诱导乳状液发生O/W(1)→W/O→O/W(2)双重相转变.     

Water mass transfer in W/O emulsions

Water transportation through the oil phase in W/O emulsions and in W1/O/W2 systems (W/O emulsion in contact with water) was examined. Substance diffusion through interfaces led to interface instability and spontaneous emulsification which caused nanodispersion formation. The photomicrographs of Pt/C replicas of emulsions showed the presence in the continuous oil phase a lot of nanodispersion droplets with a diameter in the range 17-25 nm. Diffusion coefficient (D) of water calculated on the base of Lifshiz-Slezov-Wagner (LSW) equation was about 15 times lower than the coefficients of molecular diffusion. Since such emulsions were extremely unstable toward coalescence, the growth of water droplets took place through as Ostwald ripening as coalescence. In three-phase W1/O/W2 systems diffusion of water, Rhodamine C, and ethanol was studied. D calculated on the base of the equation of nonstationary diffusion were approximately 1000 times lower than molecular ones. It was assumed, that nanodispersion droplets were more likely water carriers in investigated W/O emulsions stabilized by sorbitan monooleate.     

One-step formation of w/o/w multiple emulsions stabilized by single amphiphilic block copolymers

Multiple emulsions are complex polydispersed systems in which both oil-in-water (O/W) and water-in-oil (W/O) emulsion exists simultaneously. They are often prepared accroding to a two-step process and commonly stabilized using a combination of hydrophilic and hydrophobic surfactants. Recently, some reports have shown that multiple emulsions can also be produced through one-step method with simultaneous occurrence of catastrophic and transitional phase inversions. However, these reported multiple emulsions need surfactant blends and are usually described as transitory or temporary systems. Herein, we report a one-step phase inversion process to produce water-in-oil-in-water (W/O/W) multiple emulsions stabilized solely by a synthetic diblock copolymer. Unlike the use of small molecule surfactant combinations, block copolymer stabilized multiple emulsions are remarkably stable and show the ability to separately encapsulate both polar and nonpolar cargos. The importance of the conformation of the copolymer surfactant at the interfaces with regards to the stability of the multiple emulsions using the one-step method is discussed.     

Surfactant-Free Multiple Pickering Emulsions Stabilized by Combining Hydrophobic and Hydrophilic Nanoparticles

A series of W/O/W or O/W/O emulsion stabilized solely by two different types of solid nanoparticles were prepared by a two-step method. We explored the option of particular emulsifiers for the multiple Pickering emulsions, and a variety of nanoparticles (silica, iron oxide, and clay) only differing in their wettability was used. The primary W/O emulsion was obtained by the hydrophobic nanoparticles, and then the hydrophilic nanoparticles were used as emulsifier in the secondary emulsification to prepare the W/O/W emulsion. In a similar way, the primary O/W emulsion of the O/W/O emulsion was stabilized by the hydrophilic nanoparticles, while the secondary emulsification to prepare the O/W/O emulsion was effected with the hydrophobic nanoparticles. The resultant multiple Pickering emulsion was stable to coalescence for more than 3 months, except the W/O/W emulsions of which the secondary emulsion stabilized by clay nanoparticles became a simple O/W emulsion in a day after preparation. Moreover, the temperature and pH sensitive poly(N-isopropylacrylamide-co-methacrylic acid) (P(NIPAm-co-MAA)) microgels were introduced as an emulsifier for the secondary emulsification to obtain the stimulus-responsive multiple W/O/W emulsion. Such microgel-stabilized multiple emulsions could realize the efficient controlled release of water-soluble dye, Rhodamine B (RB) on demand in a multiple-emulsion delivery system.      

Interface composition of multiple emulsions: rheology as a probe

We have investigated the dynamic rheological properties of concentrated multiple emulsions to characterize their amphiphile composition at interfaces. Multiple emulsions (W1/O/W2) consist of water droplets (W1) dispersed into oil globules (O), which are redispersed in an external aqueous phase (W2). A small-molecule surfactant and an amphiphilic polymer were used to stabilize the inverse emulsion (W1 in oil globules) and the inverse emulsion (oil globules in W2), respectively. Rheological and interfacial tension measurements show that the polymeric surfactant adsorbed at the globule interface does not migrate to the droplet interfaces through the oil phase. This explains, at least partly, the stability improvement of multiple emulsions as polymeric surfactants are used instead of small-molecule surfactants.     

Latex-particle-stabilized emulsions of anti-Bancroft type

Here, we investigate water-in-oil (W/O) emulsions that are stabilized by polystyrene latex particles with sulfate surface groups. The particles, which play the role of emulsifier, are initially contained in the disperse (water) phase. The existence of such emulsions formally contradicts the empirical Bancroft rule. Theoretical considerations predict that the drop diameter has to be inversely proportional to the particle concentration, but should be independent of the volume fraction of water. In addition, there should be a second emulsification regime, in which the drop diameter is determined by the input mechanical energy during the homogenization. The existence of these two regimes has been experimentally confirmed, and the obtained data agree well with the theoretical model. Stable W/O emulsions have been produced with hexadecane and tetradecane, while, in the case of more viscous and polar oils (soybean and silicone oil), the particles enter into the oily phase, and Pickering emulsions cannot be obtained. The formation of stable emulsions demands the presence of a relatively high concentration of electrolyte that lowers the electrostatic barrier to particle adsorption at the oil-water interface. Because the attachment of particles at the drop surfaces represents a kind of coagulation, it turns out that the Schulze-Hardy rule for the critical concentration of coagulation is applicable also to emulsification, which has been confirmed with suspensions containing Na(+), Mg(2+), and Al(3+) counterions. The increase of the particle and electrolyte concentrations and the decrease of the volume fraction of water are other factors that facilitate emulsification in the investigated system. To quantify the combined action of these factors, an experimental stability-instability diagram has been obtained.     

MULTIPLE EMULSIONS STABILIZED BY COLLOIDAL MICROGRYSTALLINE CELLULOSE

Multiple emulsions stabilized by colloidal microcrystalline cellulose (CMCC, Avicel RC591) at the w/o and o/w interfaces, and by the addition of Span 80 or Span 85 at the w/o interface, were studied by means of brightfield microscopy, freeze-etch electron microscopy, droplet size distribution analysis and rheologic measurements. Stable multiple emulsions were prepared by incorporation of sodium chloride in the innermost aqueous phase, thereby creating an osmotic gradient preventing loss of the inner aqueous phase to the external aqueous phase. Freeze-etch electron microscopy of the multiple emulsions indicated the presence of a network of microcrystalline cellulose at the outer o/w interface. It may be assumed that the surfactant directly stabilized the w/o interface by adsorption at the interface, as well as indirectly by facilitating wetting of the microcrystalline cellulose by the oil. From rheologic measurements, the existence of a three-dimensional network in the external aqueous phase was indicated by the considerable degrees of thlxotropy and significant static yield values of these multiple emulsions.     

Copolymer microgels by precipitation polymerisation of N-vinylcaprolactam and N-isopropylacrylamides in aqueous medium

In this work, we designed copolymer microgels by the copolymerisation of N-vinylcaprolactam (VCL) and two acrylamides (N-isopropylacrylamide (NIPAAm) and N-isopropylmethacrylamide (NIPMAAm)) under precipitation conditions in aqueous phase. In synthesis protocols, the ratio between monomers was varied from 1:5 to 5:1 mol/mol. By NMR and Raman spectroscopy, we determined the chemical composition of PVCL/NIPAAm and PVCL/NIPMAAm copolymer microgels reflecting the initial monomer ratio in the reaction mixture. The hydrodynamic radii of PVCL/NIPAAm microgels are around 375 nm (at 25 °C) and do not vary with the copolymer composition. On the contrary, for PVCL/NIPMAAm microgels, the size decreases from 450 to 250 nm with an increase of the VCL amount in copolymer structure. The heterogeneity of the microgel structure in terms of the distribution of the monomer units was probed by ¹H transverse magnetization relaxation NMR, showing that the VCL, NIPAAm and NIPMAAm units are unorderly distributed in the colloidal networks. The investigation of volume phase transition temperature (VPTT) for copolymer microgels was performed using dynamic light scattering, NMR and differential scanning calorimetry. It has been found that PVCL/NIPAAm microgels show VPTT around 35 °C independently from the copolymer composition; however, PVCL/NIPMAAm particles exhibit a nonlinear increase of VPTT from 34 to 45 °C as the NIPMAAm fraction in copolymer structure increases.     

Stabilization of Water‐Soluble Antioxidant in Water‐in‐Oil‐in‐Water Double Emulsions

Abstract

In this study, we are introducing a method that can effectively stabilize antioxidants in water‐in‐oil‐in‐water (W/O/W) double emulsions. Preliminarily, stable W/O/W double emulsions were produced by manipulating the characteristics of internal aqueous phase via two‐stage emulsification, resulting consequently in the formation of fine internal water droplets in the dispersed oil droplets. From conductivity measurements that can determine the elution amount of internal aqueous phase, it was confirmed that the double emulsion stability could be improved by treating the internal aqueous phase with a hydroxypropyl‐beta‐cyclodextrin. In this study, kojic acid, 5‐hydroxy‐2‐(hydroxymethyl)‐4‐pyrone was selected as a model antioxidant. The stabilization of kojic acid was attempted by locating it in the internal water droplets of the stable W/O/W double emulsions. The stability of kojic acid in the double emulsion system could be maintained at 90% for 10 weeks at high temperature. We believe that these stable W/O/W double emulsions could be used meaningfully as a carrier for many unstable antioxidants.     

Polyols,High Pressure,and Refractive Indices Equalization for Improved Stability of W/O Emulsions for Food Applications

Mixtures of polyols (glycerol, propylene glycol, glucose) and water were emulsified in oil (isopropyl myristate (IPM), medium chain triglycerides (MCT), long chain triglycerides (LCT), and d-limonene) under elevated pressures and homogenization, in the presence of polyglycerol polyricinoleate (PGPR), glycerol monooleate (GMO), and their mixture as emulsifiers to form water-in-oil emulsions. High pressures was applied to: a) the emulsion, b) the aqueous phase and c) the oil phase in the presence of the emulsifiers (PGPR and GMO). Under optimal pressure (2000 atms) applied to the ready-made emulsion or to the aqueous phase prior to its emulsification, and with optimal composition (30wt% polyol in the aqueous phase and MCT as the oil phase), the aqueous droplets were stable for months and submicron in size (0.1 μm). Moreover, due to equalization of the oil and the aqueous phases refractive indices, the emulsions were almost transparent. Pressure and polyols have synergistic effects on the emulsions stability. During preparation, surface tensions and interfacial tensions were dramatically reduced until an optimal water/polyols ratio was achieved, which allows rupturing of the droplets to submicronal size (0.1 μm) without recoalescence and fast diffusion to the interface. These unique W/O emulsions are suitable for preparing W/O/W double emulsions for sustained release of active materials for food applications.     

Microscope measurements for the transient formation of W/O emulsions of sodium bis(2-ethylhexyl) sulfosuccinate in the dodecane/water interfacial region

The present study investigated the transient formation of water-in-oil (W/O) emulsions of sodium bis(2-ethylhexyl) sulfosuccinate (aerosol OT, AOT) in a dodecane/water interfacial region and the anomalous uptake of water in the dodecane phase by in situ bright-field optical microscopy and water concentration measurements in detail. The hydrodynamic radius of the individual W/O emulsions in the dodecane phase was determined to be 0.1-1.2 μm from the analysis of their diffusion behavior; they are much larger than common W/O microemulsions (a few nanometers in radius). At first, they were formed spontaneously in the dodecane/water interfacial region without shaking, and they diffused away into the dodecane phase. Then, almost all of them vanished at the interface by fusion. Their number and the water concentration in the dodecane phase increased first and then decreased gradually. The formation mechanism was discussed with estimated concentration profiles of AOT and water molecules, which suggests that larger W/O emulsions of 0.01-0.44 μm in radius can be formed in the dodecane phase near the interface (within 2 μm) because the concentration of AOT becomes lower than that of water there.     

Preparation of a stable double emulsion (W1/O/W2): role of the interfacial films on the stability of the system

This paper presents new protocols enabling preparation of W1/O/W2 double emulsions: one, using soybean oil as the O phase, that yields edible emulsions with industrial applications, and a second that yields emulsions with a previously unattainable concentration 15% (w/w) of surfactants in the external phase (the 15% target was chosen to meet the typical industry standard). Preparation of a stable W1/O emulsion was found to be critical for the stability of the system as a whole. Of the various low HLB primary surfactants tested, only cethyl dimethicone copolyol (Abil EM90), A-B-A block copolymer (Arlacel P135), and polyglycerol ester of ricinoleic acid (Grinstead PGR-90) yielded a stable W/O emulsion. Investigation of the surface properties of those surfactants using the monolayer technique found two significant similarities: (1) stable, compressible, and reversibly expandable monolayers; and (2) high elasticity and surface potential. The high degree of elasticity of the interfacial film between W1 and O makes it highly resilient under stress; its failure to break contributes to the stability of the emulsion. The high surface potential values observed suggest that the surfactant molecules lie flat at the O/W interfaces. In particular, in the case of PGR-90, the hydroxyl (-OH) groups on the fatty acid chains serve as anchors at the O/W interfaces and are responsible for the high surface potential. The long-term stability of the double emulsion requires a balance between the Laplace and osmotic pressures (between W1 droplets in O and between W1 droplets and the external aqueous phase W2). The presence of a thickener in the outer phase is necessary in order to reach a viscosity ratio (preferably approximately 1) between the W1/O and W2 phases, allowing dispersion of the viscous primary emulsion into the W2 aqueous phase. The thickener, which also serves as a dispersant and consequently prevents phase separation due to its thixotropic properties, must be compatible with the surfactants. Finally, the interactions between the low and high HLB emulsifiers at the O/W2 interface should not destabilize the films. It was observed that such destructive interaction for the system could be prevented by the use of two high HLB surfactants in the outer aqueous phase: an amphoteric surfactant, Betaine, and an anionic surfactant, sodium lauryl ether sulfate. The combination of such pairs of surfactants was found to contribute to the films' stability.     

Preparation and characteristics of multiple emulsions containing liquid crystals

In this paper, multiple emulsions containing liquid crystals were prepared successfully and the influence of formulation parameters on the formation mechanism was studied. Moreover, differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS) spectra analysis and stability analysis were used to characterise the property of them. The results showed that the chemical structure of water-in-oil (W/O) emulsifiers directly impacted on the formation of multiple structure, but the effect on the formation of liquid crystal structure was negligible. With the gap of the polarity between inner and outer liquid oils decreased, both multiple structure and liquid crystal structure were harder to form. The content of sodium chloride in internal aqueous phase, which should be neither too high nor too low, has great impact on the formulation of multiple structure. It was easier to form two structures simultaneously when the carbon chain length of fatty alcohols was closer to that of emulsifier C₂₂ alkyl polyglucoside (202). DSC elucidated the phase transitions of water in the liquid crystal layer and the W/O emulsions. SAXS indicated that the liquid crystal orientation was lamellar. The stability analysis showed that the presence of liquid crystal structure had a significant contribution to the stability of the multiple emulsions.     

Emulsions stabilized by stimuli-sensitive poly(N-isopropylacrylamide)-co-methacrylic acid polymers: microgels versus low molecular weight polymers

Responsive polymer microgels can be employed for the preparation of stimuli-sensitive emulsions. The microgels used in this study are based on cross-linked copolymers including N-isopropylacrylamide and methacrylic acid. We conducted the synthesis under acidic and basic conditions to investigate the effect of changes of comonomer solubility on the microgel's composition and ability to stabilize emulsions. The synthesis product was partially divided into two fractions by centrifugation. Raw product, collected supernatant, and purified microgel were characterized by means of light scattering, titration, as well as electrophoretic mobility. The ability of the three components to act as stabilizers was investigated by preparing the octanol/water emulsions and looking at their response to pH and temperature changes. The interfacial activity of the three components was characterized by means of the pendent drop technique. Furthermore, we investigated the response of the interface to dilatational stress using a pendant drop tensiometer equipped with an oscillating drop module. The results demonstrate that the pH during synthesis has a significant impact on the composition and thus the properties of the microgel and its ability to be utilized as a stimuli responsive stabilizer for emulsions. We conclude that microgels can be used as stimuli-sensitive stabilizers for emulsions, if the charges are incorporated in the microgel itself.