The effects of surfactant and oil chemical structures on self-assembly in apolar media.

The thermodynamic and chemical structural aspects of surfactant self-assembly in aqueous systems have been much studied. On the other hand, for oil-water interfaces the effects of chemical structures of surfactants and solvents have received less attention. This review focuses on the surfactant chemical effects in low dielectric solvents, in particular formation and properties of surfactant films at oil-water interfaces. For this purpose, reversed micelles (RMs) and water-in-oil (W/O) microemulsions (µEs) serve as model systems, since electrostatic effects are minimized, allowing a focus on chain architecture of the surfactants and oil solvents themselves. It is noted that chemical structure can have profound effects on stability and self-assembly, suggesting a possibility of identifying unified chemical principles for designing and formulating systems across various thermodynamic conditions.

A guide to designing graphene-philic surfactants.

HYPOTHESIS: As compared to common aliphatic surfactants, increasing the number of pendant or incorporated aromatic groups in a surfactant is expected to offer significant enhancement in the affinity for graphene surfaces. The basis for enhanced graphene-philicity of aromatic surfactants is that they can develop appreciable π - π interactions with graphene. Furthermore, charged (anionic) surfactants are expected to confer electrostatic stabilization on surfactant-graphene composites. Hence, it is expected that anionic aromatic surfactants combine these two properties for effective stabilization of graphene dispersions in water. EXPERIMENTAL: The properties of two custom made graphene-compatible surfactants carrying two and three aromatic moieties in the hydrophobic tails, namely DC3Ph2 (sodium 1,4-dioxo-1,4-bis(3-phenylpropoxy)butane-2-sulfonate) and TC3Ph3 (sodium 1,5-dioxo-1,5-bis(3-phenylpropoxy)-3-((3-phenylpropoxy)carbonyl) pentane-2-sulfonate) were compared with other common ionic commercial surfactants. Air-water (a/w) surface tension measurements were used to assess the surfactant adsorption and interfacial packing in the absence and presence of graphene. The surfactant coverage index for graphene (Ф) was calculated using surfactant headgroup areas derived from a/w surface tension data, chain volumes, and molecular fragment volumes from literature. FINDINGS: Increasing the number of aromatic groups and tails per surfactant was shown to increase the ability of surfactants to pack and fill space, as expressed by Ф. Comparison between the values of Ф for surfactants of different chain structure and architecture showed that the affinity for graphene increased with Ф. Hence, there is an implicit link between surfactant-graphene compatibility and the identity, chemical composition and architecture of the surfactant chains.

Fabrication and application of composite adsorbents made by one-pot electrochemical exfoliation of graphite in surfactant ionic liquid/nanocellulose mixtures.

Previously, surfactant-assisted exfoliated graphene oxide (sEGO) formed with the triple-chain surfactant TC14 (sodium 1,4-bis(neopentyloxy)-3-(neopentylcarbonyl)-1,4-dioxobutane-2-sulfonate) was applied in wastewater treatment. The extent of dye-removal and the adsorption capacity of the sEGO formed with this triple-chain surfactant outperformed those of two other systems, namely, the di-chain version of TC14 (AOT14; sodium 1,2-bis-(2,2-dimethyl-propoxycarbonyl)-ethanesulfonate) and the single-chain surfactant sodium n-dodecylsulfate. In the present study, to further optimise the surfactant chemical structure, the sodium ion of TC14 was substituted with 1-butyl-3-methyl-imidazolium (BMIM) generating surfactant ionic liquids (SAILs; 1-butyl-3-imidazolium 1,4-bis(neopentyloxy)-3-(neopentyloxycarbonyl)-1,4-dioxobutane-2-sulfonate), hereafter denoted as BMIM-TC14. This SAIL, together with nanofibrillated kenaf cellulose (NFC), was used to electrochemically exfoliate graphite, yielding BMIM-TC14 sEGO/NFC composites. These highly hydrophobic polymer composites were then used for the removal of methylene blue (MB) from aqueous solution. 1H NMR spectroscopy was used to elucidate the structure of the synthesised SAILs. The morphologies of the resulting nanocomposites were investigated using Raman spectroscopy, field-emission scanning electron microscopy, and high-resolution transmission electron microscopy. Analysis using small-angle neutron scattering was performed to examine the aggregation behaviour of sEGO and custom-made SAILs. Zeta potential, surface tension, and dynamic light-scattering measurements were used to study the aqueous properties and colloidal stability of the suspension. Amongst the surfactants tested, BMIM-TC14 sEGO/NFC exhibited the highest MB adsorption ability, achieving 99% dye removal under optimum conditions. These results highlight the importance of modifying the hydrophilic moieties of amphiphilic compounds to improve the performance of sEGO/NFC composites as effective adsorbents for wastewater treatment.

Design of Surfactant Tails for Effective Surface Tension Reduction and Micellization in Water and/or Supercritical CO2.

The interfacial properties and water-in-CO2 (W/CO2) microemulsion (µE) formation with double- and novel triple-tail surfactants bearing trimethylsilyl (TMS) groups in the tails are investigated. Comparisons of these properties are made with those for analogous hydrocarbon (HC) and fluorocarbon (FC) tail surfactants. Surface tension measurements allowed for critical micelle concentrations (CMC) and surface tensions at the CMC (γCMC) to be determined, resulting in the following trend in surface activity FC > TMS > HC. Addition of a third surfactant tail gave rise to increased surface activity, and very low γCMC values were recorded for the double/triple-tail TMS and HC surfactants. Comparing effective tail group densities (ρlayer) of the respective surfactants allowed for an understanding of how γCMC is affected by both the number of surfactant tails and the chemistry of the tails. These results highlight the important role of tail group chemical structure on ρlayer for double-tail surfactants. For triple-tail surfactants, however, the degree to which ρlayer is affected by tail group architecture is harder to discern due to formation of highly dense layers. Stable W/CO2 µEs were formed by both the double- and the triple-tail TMS surfactants. High-pressure small-angle neutron scattering (HP-SANS) has been used to characterize the nanostructures of W/CO2 µEs formed by the double- and triple-tail surfactants, and at constant pressure and temperature, the aqueous cores of the microemulsions were found to swell with increasing water-to-surfactant ratio (W0). A maximum W0 value of 25 was recorded for the triple-tail TMS surfactant, which is very rare for nonfluorinated surfactants. These data therefore highlight important parameters required to design fluorine-free environmentally responsible surfactants for stabilizing W/CO2 µEs.

Water-in-CO2 Microemulsions Stabilized by an Efficient Catanionic Surfactant.

To facilitate potential applications of water-in-supercritical CO2 microemulsions (W/CO2 µEs) efficient and environmentally responsible surfactants are required with low levels of fluorination. As well as being able to stabilize water-CO2 interfaces, these surfactants must also be economical, prevent bioaccumulation and strong adhesion, deactivation of enzymes, and be tolerant to high salt environments. Recently, an ion paired catanionic surfactant with environmentally acceptable fluorinated C6 tails was found to be very effective at stabilizing W/CO2 µEs with high water-to-surfactant molar ratios (W0) up to ∼50 (Sagisaka, M.; et al. Langmuir 2019, 35, 3445-3454). As the cationic and anionic constituent surfactants alone did not stabilize W/CO2 µEs, this was the first demonstration of surfactant synergistic effects in W/CO2 microemulsions. The aim of this new study is to understand the origin of these intriguing effects by detailed investigations of nanostructure in W/CO2 microemulsions using high-pressure small-angle neutron scattering (HP-SANS). These HP-SANS experiments have been used to determine the headgroup interfacial area and volume, aggregation number, and effective packing parameter (EPP). These SANS data suggest the effectiveness of this surfactant originates from increased EPP and decreased hydrophilic/CO2-philic balance, related to a reduced effective headgroup ionicity. This surfactant bears separate C6F13 tails and oppositely charged headgroups, and was found to have a EPP value similar to that of a double C4F9-tail anionic surfactant (4FG(EO)2), which was previously reported to be one of most efficient stabilizers for W/CO2 µEs (maximum W0 = 60-80). Catanionic surfactants based on this new design will be key for generating superefficient W/CO2 µEs with high stability and water solubilization.

Highly branched triple-chain surfactant-mediated electrochemical exfoliation of graphite to obtain graphene oxide: colloidal behaviour and application in water treatment.

The generation of surfactant-assisted exfoliated graphene oxide (sEGO) by electrochemical exfoliation is influenced by the presence of surfactants, and in particular the hydrophobic tail molecular-architecture. Increasing surfactant chain branching may improve the affinity for the graphite surfaces to provide enhanced intersheet separation and stabilisation of exfoliated sheets. The resulting sEGO composites can be readily used to remove of a model pollutant, the dye, methylene blue (MB), from aqueous solutions by providing abundant sites for dye adsorption. This article explores relationships between surfactant structure and the performance of sEGO for MB adsorption. Double-branched and highly branched triple-chain graphene-compatible surfactants were successfully synthesised and characterised by 1H NMR spectroscopy. These surfactants were used to produce sEGO via electrochemical exfoliation of graphite, and the sEGOs generated were further utilised in batch adsorption studies of MB from aqueous solutions. The properties of these synthesised surfactants were compared with those of a common single-chain standard surfactant, sodium dodecyl-sulfate (SDS). The structural morphology of sEGO was assessed using Raman spectroscopy and field emission scanning electron microscopy (FESEM). To reveal the links between the hydrophobic chain structure and the sEGO adsorption capacity, UV-visible spectroscopy, zeta potential, and air-water (a/w) surface tension measurements were conducted. The aggregation behaviour of the surfactants was studied using small-angle neutron scattering (SANS). The highly branched triple-chain surfactant sodium 1,4-bis(neopentyloxy)-3-(neopentylcarbonyl)-1,4-dioxobutane-2-sulfonate (TC14) displayed enhanced exfoliating efficiency compared to those of the single-and double-chain surfactants, leading to ∼83% MB removal. The findings suggest that highly branched triple-chain surfactants are able to offer more adsorption sites, by expanding the sEGO interlayer gap for MB adsorption, compared to standard single-chain surfactants.

Electrochemical exfoliation of graphite in nanofibrillated kenaf cellulose (NFC)/surfactant mixture for the development of conductive paper.

The effect of incorporating common dodecyl anionic and cationic surfactants such as dodecyltrimethylammonium bromide (DTAB), dodecylethyldimethylammonium bromide (DDAB), and sodium dodecylsulfate (SDS) in nanocomposites of reduced graphene oxide and nanocellulose are described. The stabilization and electrical properties of the nanocomoposites of reduced graphene oxide (RGO) and nanofibrillated kenaf cellulose (NFC) were characterized using four-point probe electrical conductivity measurements. Raman spectroscopy, field emission scanning electron microscopy, and high-resolution transmission electron microscopy were used to investigate dispersion morphology and the quality of RGO inside the NFC matrices. Small-angle neutron scattering (SANS) was used to study the aggregation behavior of the aqueous surfactant systems and RGO dispersions. The cationic surfactant DTAB proved to be the best choice for stabilization of RGO in NFC, giving enhanced electrical conductivity five orders of magnitude higher than the neat NFC. The results highlight the effects of hydrophilic surfactant moieties on the structure, stability and properties of RGO/NFC composites.

Self-assembled nanostructures in ionic liquids facilitate charge storage at electrified interfaces.

Driven by the potential applications of ionic liquids (ILs) in many emerging electrochemical technologies, recent research efforts have been directed at understanding the complex ion ordering in these systems, to uncover novel energy storage mechanisms at IL-electrode interfaces. Here, we discover that surface-active ILs (SAILs), which contain amphiphilic structures inducing self-assembly, exhibit enhanced charge storage performance at electrified surfaces. Unlike conventional non-amphiphilic ILs, for which ion distribution is dominated by Coulombic interactions, SAILs exhibit significant and competing van der Waals interactions owing to the non-polar surfactant tails, leading to unusual interfacial ion distributions. We reveal that, at an intermediate degree of electrode polarization, SAILs display optimum performance, because the low-charge-density alkyl tails are effectively excluded from the electrode surfaces, whereas the formation of non-polar domains along the surface suppresses undesired overscreening effects. This work represents a crucial step towards understanding the unique interfacial behaviour and electrochemical properties of amphiphilic liquid systems showing long-range ordering, and offers insights into the design principles for high-energy-density electrolytes based on spontaneous self-assembly behaviour.

Surfactants with aromatic headgroups for optimizing properties of graphene/natural rubber latex composites (NRL): Surfactants with aromatic amine polar heads.

HYPOTHESIS: The compatibility of surfactants and graphene surfaces can be improved by increasing the number of aromatic groups in the surfactants. Including aniline in the structure may improve the compatibility between surfactant and graphene further still. Surfactants can be modified by incorporating aromatic groups in the hydrophobic chains or hydrophilic headgroups. Therefore, it is of interest to investigate the effects of employing anilinium based surfactants to disperse graphene nanoplatelets (GNPs) in natural rubber latex (NRL) for the fabrication of electrically conductive nanocomposites. EXPERIMENTS: New graphene-philic surfactants carrying aromatic moieties in the hydrophilic headgroups and hydrophobic tails were synthesized by swapping the traditional sodium counterion with anilinium. 1H NMR spectroscopy was used to characterize the surfactants. These custom-made surfactants were used to assist the dispersion of GNPs in natural rubber latex matrices for the preparation of conductive nanocomposites. The properties of nanocomposites with the new anilinium surfactants were compared with commercial sodium surfactant sodium dodecylsulfate (SDS), sodium dodecylbenzenesulfonate (SDBS), and the previously synthesized aromatic tri-chain sodium surfactant TC3Ph3 (sodium 1,5-dioxo-1,5-bis(3-phenylpropoxy)-3-((3phenylpropoxy)carbonyl) pentane-2-sulfonate). Structural properties of the nanocomposites were studied using Raman spectroscopy, field emission scanning electron microscopy (FESEM), and high-resolution transmission electron microscopy (HRTEM). Electrical conductivity measurements and Zeta potential measurements were used to assess the relationships between total number of aromatic groups in the surfactant molecular structure and nanocomposite properties. The self-assembly structure of surfactants in aqueous systems and GNP dispersions was assessed using small-angle neutron scattering (SANS). FINDINGS: Among these different surfactants, the anilinium version of TC3Ph3 namely TC3Ph3-AN (anilinium 1,5-dioxo-1,5-bis(3-phenylpropoxy)-3-((3phenylpropoxy)carbonyl) pentane-2-sulfonate) was shown to be highly efficient for dispersing GNPs in the NRL matrices, increasing electrical conductivity eleven orders of magnitude higher than the neat rubber latex. Comparisons between the sodium and anilinium surfactants show significant differences in the final properties of the nanocomposites. In general, the strategy of increasing the number of surfactant-borne aromatic groups by incorporating anilinium ions in surfactant headgroups appears to be effective.

Water-in-CO2 Microemulsions Stabilized by Fluorinated Cation-Anion Surfactant Pairs.

High-water-content water-in-supercritical CO2 (W/CO2) microemulsions are considered to be green, universal solvents, having both polar and nonpolar domains. Unfortunately, these systems generally require environmentally unacceptable stabilizers like long and/or multifluorocarbon-tail surfactants. Here, a series of catanionic surfactants having more environmentally friendly fluorinated C4-C6 tails have been studied in terms of interfacial properties, aggregation behavior, and solubilizing power in water and/or CO2. Surface tensions and critical micelle concentrations of these catanionic surfactants are, respectively, lowered by ∼9 mN/m and 100 times than those of the constituent single fluorocarbon-tail surfactants. Disklike micelles in water were observed above the respective critical micelle concentrations, implying the catanionic surfactants have a high critical packing parameter, which should be suitable for the formation of reverse micelles. Based on visual observation of phase behavior and Fourier transform infrared spectroscopic and small-angle neutron scattering studies, one of the three catanionic surfactants tested was found to form transparent single-phase W/CO2 microemulsions with a water-to-surfactant molar ratio of up to ∼50. This is the first successful demonstration of the formation of W/CO2 microemulsions by synergistic ion-pairing of anionic and cationic single-tail surfactants. This indicates that catanionic surfactants offer a promising approach to generate high-water-content W/CO2 microemulsions.

Preparation of conductive cellulose paper through electrochemical exfoliation of graphite: The role of anionic surfactant ionic liquids as exfoliating and stabilizing agents.

A facile electrochemical exfoliation method was established to efficiently prepare conductive paper containing reduced graphene oxide (RGO) with the help of single chain anionic surfactant ionic liquids (SAILs). The surfactant ionic liquids are synthesized from conventional organic surfactant anions and a 1-butyl-3-methyl-imidazolium cation. For the first time the combination of SAILs and cellulose was used to directly exfoliate graphite. The ionic liquid 1-butyl-3-methyl-imidazolium dodecylbenzenesulfonate (BMIM-DBS) was shown to have notable affinity for graphene, demonstrating improved electrical properties of the conductive cellulose paper. The presence of BMIM-DBS in the system promotes five orders of magnitude enhancement of the paper electrical conductivity (2.71 × 10-5 S cm-1) compared to the native cellulose (1.97 × 10-10 S cm-1). A thorough investigation using electron microscopy and Raman spectroscopy highlights the presence of uniform graphene incorporated inside the matrices. Studies into aqueous aggregation behavior using small-angle neutron scattering (SANS) point to the ability of this compound to act as a bridge between graphene and cellulose, and is responsible for the enhanced exfoliation level and stabilization of the resulting dispersion. The simple and feasible process for producing conductive paper described here is attractive for the possibility of scaling-up this technique for mass production of conductive composites containing graphene or other layered materials.

Surface and bulk properties of surfactants used in fire-fighting.

HYPOTHESIS: Reports on the colloidal and interfacial properties of fluorocarbon (FC) surfactants used in fire-fighting foam formulations are rare. This is primarily because these formulations are complex mixtures of different hydrocarbon (HC) and fluorocarbon (FC) surfactants. By developing a greater understanding of the individual properties of these commercial FC surfactants, links can be made between structure and respective surface/ bulk behaviour. Improved understanding of structure property relationships of FC surfactants will therefore facilitate the design of more environmentally responsible surfactant replacements. EXPERIMENTS: Surface properties of three partially fluorinated technical grade surfactants were determined using tensiometry and neutron reflection (NR), and compared with a research-grade reference surfactant (sodium perfluorooctanoate (NaPFO)). To investigate the bulk behaviour and self-assembly in solution, small-angle neutron (SANS) scattering was used. FINDINGS: All FC surfactants in this study generate very low surface tensions (< 20 mN m-1) which are comparable, and in some cases, lower than fully-fluorinated surfactant analogues. The complementary techniques (tensiometry and NR) allowed direct comparison to be made with NaPFO in terms of adsorption parameters such as surface excess and area per molecule. Surface tension data for these technical grade FC surfactants were not amenable to reliable interpretation using the Gibbs adsorption equation, however NR provided reliable results. SANS has highlighted how changes in surfactant head group structure can affect bulk properties. This work therefore provides fresh insight into the structure property relationships of some industrially relevant FC surfactants, highlighting properties which are essential for development of more environmentally friendly replacements.

Self-Assembled Magnetic Viruslike Particles for Encapsulation and Delivery of Deoxyribonucleic Acid.

Developing nontoxic artificial carriers for stimuli-responsive capture, transport, and delivery of biomolecules is of immense scientific interest. Herein, for the first time, we synthesize a double-tailed cationic surfactant, (C16H33)2(CH3)2N+[FeCl3Br]-, which possesses magnetic properties [magnetic surfactants (Mag-Surfs)]. The time-dependent formation of virus-shaped hybrid mixed assemblies of polyoxometalates (POMs) {Mo72Fe30}/Mag-Surf with hollow-shell structures is followed. These structures serve well as robust high-surface-area shuttles, which can be manipulated with applied magnetic fields. By using cationic Mag-Surfs, the anionic POMs and DNA can be complexed in these ternary mixtures. These virus-shaped complexes act as nanoanchors and nanomotors, which can be utilized for binding, anchoring, and delivery of biomolecules, such as DNA. It is found that they have a good absorption capacity for DNA and myoglobin over 24 h, after application of a magnetic field. The realization of magnetic virus-shaped {Mo72Fe30}/Mag-Surf spheres may open possibilities for designing other functional nanoparticles, allowing effective control over the delivery/separation of biomolecules.

Conversion of "Waste Plastic" into Photocatalytic Nanofoams for Environmental Remediation.

Plastic debris is a major environmental concern, and to find effective ways to reuse polystyrene (PS) presents major challenges. Here, it is demonstrated that polystyrene foams impregnated with SnO2 are easily generated from plastic debris and can be applied to photocatalytic degradation of dyes. SnO2 nanoparticles were synthesized by a polymeric precursor method, yielding specific surface areas of 15 m2/g after heat treatment to 700 °C. Crystallinity, size, and shape of the SnO2 particles were assessed by X-ray diffraction (XRD) and transmission electron microscopy (TEM), demonstrating the preparation of crystalline spherical nanoparticles with sizes around 20 nm. When incorporated into PS foams, which were generated using a thermally induced phase separation (TIPS) process, the specific surface area increased to 48 m2/g. These PS/SnO2 nanofoams showed very good efficiency for photodegradation of rhodamine B, under UV irradiation, achieving up to 98.2% removal. In addition the PS/SnO2 nanofoams are shown to retain photocatalytic activity for up to five reuse cycles.

Rational design of aromatic surfactants for graphene/natural rubber latex nanocomposites with enhanced electrical conductivity.

HYPOTHESIS: Graphene nanoplatelets (GNPs) can be dispersed in natural rubber matrices using surfactants. The stability and properties of these composites can be optimized by the choice of surfactants employed as stabilizers. Surfactants can be designed and synthesized to have enhanced compatibility with GNPs as compared to commercially available common surfactants. Including aromatic groups in the hydrophobic chain termini improves graphene compatibility of surfactants, which is expected to increase with the number of aromatic moieties per surfactant molecule. Hence, it is of interest to study the relationship between molecular structure, dispersion stability and electrical conductivity enhancement for single-, double-, and triple-chain anionic graphene-compatible surfactants. EXPERIMENTS: Graphene-philic surfactants, bearing two and three chains phenylated at their chain termini, were synthesized and characterized by proton nuclear magnetic resonance (1H NMR) spectroscopy. These were used to formulate and stabilize dispersion of GNPs in natural rubber latex matrices, and the properties of systems comprising the new phenyl-surfactants were compared with commercially available surfactants, sodium dodecylsulfate (SDS) and sodium dodecylbenzenesulfonate (SDBS). Raman spectroscopy, field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), and high-resolution transmission electron microscopy (HRTEM) were used to study structural properties of the materials. Electrical conductivity measurements and Zeta potential measurements were used to assess the relationships between surfactant architecture and nanocomposite properties. Small-angle neutron scattering (SANS) was used to study self-assembly structure of surfactants. FINDINGS: Of these different surfactants, the tri-chain aromatic surfactant TC3Ph3 (sodium 1,5-dioxo-1,5-bis(3-phenylpropoxy)-3-((3phenylpropoxy)carbonyl) pentane-2-sulfonate) was shown to be highly graphene-compatible (nanocomposite electrical conductivity = 2.22 × 10-5 S cm-1), demonstrating enhanced electrical conductivity over nine orders of magnitude higher than neat natural rubber-latex matrix (1.51 × 10-14 S cm-1). Varying the number of aromatic moieties in the surfactants appears to cause significant differences to the final properties of the nanocomposites.

Anisotropic reversed micelles with fluorocarbon-hydrocarbon hybrid surfactants in supercritical CO2.

Previous work (M. Sagisaka, et al. Langmuir 31 (2015) 7479-7487), showed the most effective fluorocarbon (FC) and hydrocarbon (HC) chain lengths in the hybrid surfactants FCm-HCn (sodium 1-oxo-1-[4-(perfluoroalkyl)phenyl]alkane-2-sulfonates, where m = FC length and n = HC length) were m and n = 6 and 4 for water solubilization, whereas m 6 and n 6, or m 6 and n 5, were optimal chain lengths for reversed micelle elongation in supercritical CO2. To clarify why this difference of only a few methylene chain units is so effective at tuning the solubilizing power and reversed micelle morphology, nanostructures of water-in-CO2 (W/CO2) microemulsions were investigated by high-pressure small-angle neutron scattering (SANS) measurements at different water-to-surfactant molar ratios (W0) and surfactant concentrations. By modelling SANS profiles with cylindrical and ellipsoidal form factors, the FC6-HCn/W/CO2 microemulsions were found to increase in size with increasing W0 and surfactant concentration. Ellipsoidal cross-sectional radii of the FC6-HC4/W/CO2 microemulsion droplets increased linearly with W0, and finally reached ∼39 Šand ∼78 Šat W0 = 85 (close to the upper limit of solubilizing power). These systems appear to be the largest W/CO2 microemulsion droplets ever reported. The aqueous domains of FC6-HC6 rod-like reversed micelles increased in size by 3.5 times on increasing surfactant concentration from 35 mM to 50 mM: at 35 mM, FC6-HC5 formed rod-like reversed micelles 5.3 times larger than FC6-HC6. Interestingly, these results suggest that hybrid HC-chains partition into the microemulsion aqueous cores with the sulfonate headgroups, or at the W/CO2 interfaces, and so play important roles for tuning the W/CO2 interfacial curvature. The super-efficient W/CO2-type solubilizer FC6-HC4, and the rod-like reversed micelle forming surfactant FC6-HC5, represent the most successful cases of low fluorine content additives. These surfactants facilitate VOC-free, effective and energy-saving CO2 solvent systems for applications such as extraction, dyeing, dry cleaning, metal-plating, enhanced oil recovery and organic/inorganic or nanomaterial synthesis.

Charging Poly(methyl Methacrylate) Latexes in Nonpolar Solvents: Effect of Particle Concentration.

The electrophoresis of a well-established model system of charged colloids in nonpolar solvents has been studied as a function of particle volume fraction at constant surfactant concentration. Dispersions of poly(12-hydroxystearic acid)-stabilized poly(methyl methacrylate) (PMMA) latexes in dodecane were prepared with added Aerosol OT surfactant as the charging agent. The electrophoretic mobility (µ) of the PMMA latexes is found to decrease with particle concentration. The particles are charged by a small molecule charging agent (AOT) at finite concentration, and this makes the origin of this decrease in µ unclear. There are two suggested explanations. The decrease could either be due to the reservoir of available surfactant being exhausted at high particle concentrations or the interactions between the charged particles at high particle number concentrations. Contrast-variation small-angle neutron scattering measurements of PMMA latexes and deuterated AOT-d34 surfactant in latex core contrast-matched solvent were used to study the former, and electrokinetic modeling was used to study the latter. As the same amount of AOT-d34 is found to be incorporated with the latexes at all volume fractions, the solvodynamic and electrical interactions between particles are determined to be the explanation for the decrease in mobility. These measurements show that, for small latexes, there are interactions between the charged particles at all accessible particle volume fractions and that it is necessary to account for this to accurately determine the electrokinetic ζ potential.

Electrolyte-induced Instability of Colloidal Dispersions in Nonpolar Solvents.

Dispersions of poly(methyl methacrylate) (PMMA) latexes were prepared in a low dielectric, nonpolar solvent (dodecane) both with and without the oil-soluble electrolyte, tetradodecylammonium-tetrakis(3,5-bis(trifluoromethyl)phenyl)borate. For dispersions with a high concentration of background electrolyte, the latexes become colloidally unstable and sediment in a short period of time (<1 h). This is completely reversible upon dilution. Instability of the dispersions is due to an apparent attraction between the colloids, directly observed using optical tweezers by bringing optically trapped particles into close proximity. Simple explanations generally used by colloid scientists to explain loss of stability (charge screening or stabilizer collapse) are insufficient to explain this observation. This unexpected interaction seems, therefore, to be a consequence of the materials that can be dispersed in low dielectric media and is expected to have ramifications for studying colloids in such solvents.