Spreading of aqueous surfactant solutions on oil substrates: Superspreaders vs non-superspreaders.

HYPOTHESIS: The question of why aqueous solutions of some surfactants demonstrate a rapid spreading (superspreading) over hydrophobic solid substrates, while solutions of other similar surfactants do not, has no definitive explanation despite numerous previous studies. The suggested hypothesis for this study assumes that once the spreading coefficient of surfactant is positive, there is a concentration range for solutions of any surfactant which demonstrates rapid spreading. As it is impossible to calculate spreading coefficients for solid substrates, we compare the spreading performance of known superspreaders and non-superspreaders on liquid (oil) substrate. EXPERIMENTS: The kinetics of spreading of aqueous solutions of a series of branched ionic surfactants and non-ionic trisiloxane surfactants on two liquid substrates was studied and compared with the spreading of a surfactant-free liquid, silicone oil. Both dynamic and equilibrium spreading coefficients were calculated using measured surface and interfacial tensions. FINDINGS: There is no difference in spreading rate on liquid substrate between solutions of surfactants proven as superspreaders (while spreading on solid substrate) or non-superspreaders. A rapid spreading (superspreading) with the characteristic rate of spreading O(102-103) mm2/s occurs if the dynamic spreading coefficients exceeds the positive threshold value. If the dynamic spreading coefficient is negative or slightly positive, complete wetting still occurs, but the spreading is slow with the spreading rate is O(1) mm2/s. Spreading exponents for surfactant solutions in the rapid spreading regime are considerably larger than for the surfactant-free liquid. A number of spreading and dewetting patterns were observed depending on the surfactant type, its concentration and substrate.

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.

Linear symmetric liquid crystal trimers exhibiting supramolecular chiral architectures.

We prepared a homologous series of achiral liquid crystal trimers (I-n) in which two phenylpyrimidine units and one biphenyl unit were connected via flexible spacers, and investigated the physical properties. All the trimers possessing odd-numbered methylene spacers exhibited soft crystalline chiral conglomerate phases. X-ray diffraction measurements reveal that they have an intercalated layer structure. On the other hand, the trimers possessing even-numbered spacers showed nematic and smectic C phases. We investigated the surface structures of odd-membered trimers in the soft crystalline phases using scanning electron microscopy. Trimers I-3 and I-5 were found to form cylindrical tubes, whereas trimers I-7, I-9 and I-11 toroidal pits. We discuss the formation of diverse supramolecular architectures in terms of the anisotropy of the chirality transfer.

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.

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.

Trimethylsilyl hedgehogs - a novel class of super-efficient hydrocarbon surfactants.

Presented here are the results for a novel class of hydrocarbon surfactants, termed trimethylsilyl hedgehogs (TMS-hedgehogs), due to the presence of silicon in the tails. By comparing the surface properties of these hybrid hedgehogs to purely hydrocarbon equivalents, links between performance and the structure are made. Namely, by controlling the molecular volume of the surfactant fragments, improvements can be made in surface coverage, generating lower surface energy monolayers. Small-angle neutron scattering (SANS) data have been collected showing that these novel surfactants aggregate to form ellipsoidal micelles which grow with increasing concentration. This study highlights the sensitive relationship between surface tension and the surfactant chain, for designing new super-efficient surfactants close to the limit of the lowest surface tensions possible.

Purification and characterization of a novel extracellular neutral metalloprotease from Cerrena albocinnamomea.

We selected a fungus secreting a neutral protease from soil and identified it as the basidiomycete fungus Cerrena albocinnamomea according to its ITS-5.8S rDNA and 28S rDNA-D1/D2 sequences. A major extracellular protease isolated from C. albocinnamomea was purified approximately 44-fold through two purification steps. SDS-PAGE analyses of the purified protease revealed a single band, and its molecular mass of 39,756 Da was determined using MALDI-TOF-MS. The enzyme was optimally active at approximately pH 7.0 and 45°C. The Km and Vmax values for the hydrolysis of azocasein were 2.46 mg/mL and 989 units/min/mg protein, respectively. The enzyme was stable at pH 3.6-8.6 for 16 h and at temperatures ≤35°C for 1 h. Enzymatic activity was completely inhibited by Cu2+ and Zn2+ and markedly by EDTA and phosphoramidon. The N-terminal amino acid sequence ASYRVLPIT is highly similar to those of the members of the metalloprotease family M36, such as keratinase and elastinase. However, the protease did not detectably hydrolyze keratin or elastin. In contrast, the protease hydrolyzed fibrinogen, although there were no significant sequence similarities to the N-terminal amino acid sequences of other fibrinolytic enzymes. These results suggest that the purified protease represents a new neutral metalloprotease with fibrinogenolytic activity.

New Class of Amphiphiles Designed for Use in Water-in-Supercritical CO2 Microemulsions.

Water-in-supercritical CO2 microemulsions formed using the hybrid F-H surfactant sodium 1-oxo-1-[4-(perfluorohexyl)phenyl]hexane-2-sulfonate, FC6-HC4, have recently been shown to have the highest water-solubilizing power ever reported. FC6-HC4 demonstrated the ability to outperform not only other surfactants but also other FCm-HCn analogues containing different fluorocarbon and hydrocarbon chain lengths (Sagisaka, M. et al. Langmuir 2015, 31, 7479-7487). With the aim of clarifying the key structural features of this surfactant, this study examined the phase behavior and water/supercritical CO2 aggregate formation of 1-oxo-1-[4-(perfluorohexyl)phenyl]hexane (Nohead FC6-HC4), which is an FC6-HC4 analogue but now, interestingly, without the sulfonate headgroup. Surprisingly, Nohead FC6-HC4, which would not normally be identified as a classic surfactant, yielded transparent single-phase W/CO2 microemulsions with polar cores able to solubilize a water-soluble dye, even at pressures and temperatures so low as to approach the critical point of CO2 (e.g., ∼100 bar at 35 °C). High-pressure small-angle scattering (SANS) measurements revealed the transparent phases to consist of ellipsoidal nanodroplets of water. The morphology of these droplets was shown to be dependent on the pressure, Nohead FC6-HC4 concentration, and water-to-surfactant molar ratio. Despite having almost the same structure as Nohead FC6-HC4, analogues containing both shorter and longer hydrocarbons were unable to form W/CO2 microemulsion droplets. This shows the importance of the role of the hydrocarbon chain in the stabilization of W/CO2 microemulsions. A detailed examination of the mechanism of Nohead FC6-HC4 adsorption onto the water surface suggests that the hexanoyl group protrudes into the aqueous core, allowing for association between the carbonyl group and water.

Graphene-philic surfactants for nanocomposites in latex technology.

Graphene is the newest member of the carbon family, and has revolutionized materials science especially in the field of polymer nanocomposites. However, agglomeration and uniform dispersion remains an Achilles' heel (even an elephant in the room), hampering the optimization of this material for practical applications. Chemical functionalization of graphene can overcome these hurdles but is often rather disruptive to the extended pi-conjugation, altering the desired physical and electronic properties. Employing surfactants as stabilizing agents in latex technology circumvents the need for chemical modification allowing for the formation of nanocomposites with retained graphene properties. This article reviews the recent progress in the use of surfactants and polymers to prepare graphene/polymer nanocomposites via latex technology. Of special interest here are surfactant structure-performance relationships, as well as background on the roles surfactant-graphene interactions for promoting stabilization.

Shape Modification of Water-in-CO2 Microemulsion Droplets through Mixing of Hydrocarbon and Fluorocarbon Amphiphiles.

An oxygen-rich hydrocarbon (HC) amphiphile has been developed as an additive for supercritical CO2 (scCO2). The effects of this custom-designed amphiphile have been studied in water-in-CO2 (w/c) microemulsions stabilized by analogous fluorocarbon (FC) surfactants, nFG(EO)2, which are known to form spherical w/c microemulsion droplets. By applying contrast-variation small-angle neutron scattering (CV-SANS), evidence has been obtained for anisotropic structures in the mixed systems. The shape transition is attributed to the hydrocarbon additive, which modifies the curvature of the mixed surfactant films. This can be considered as a potential method to enhance physicochemical properties of scCO2 through elongation of w/c microemulsion droplets. More importantly, by studying self-assembly in these mixed systems, fundamental understanding can be developed on the packing of HC and FC amphiphiles at water/CO2 interfaces. This provides guidelines for the design of fluorine-free CO2 active surfactants, and therefore, practical industrial scale applications of scCO2 could be achieved.

Periodic Formation/Breakdown of Lamellar Aggregates with Anionic Cyanobiphenyl Surfactants.

This study reports unusual behavior of aqueous-phase lamellar aggregates with a new class of hybrid surfactant, CB-B2ES, having mesogenic units {6-[4-(4-cyanophenyl)phenyloxy]hexyl} and temperature-sensitive oxyethylated (butoxyethoxyethyl) tails. These tails are poorly miscible and likely to microsegregate if the surfactant molecules assemble. Lamellar aggregates appear at CB-B2ES concentrations higher than 5 wt % and were found to undergo repeat formation/breakdown periodically at 30 °C, with an average domain lifetime of ∼10 s. To investigate effects of the temperature-sensitive oxyethylene units on the hydrophilic/lipophilic balance (HLB) of the CB-B2ES bilayers, a fluorescence probe 1-pyrene-carboxaldehide was solubilized in the mixtures to sense the micro-environmental polarities. Fluorimetric measurements suggested that the polarity of CB-B2ES bilayers is very similar to that of the non-ethoxylated CB-B2ES analogue at high temperatures (≥65 °C). However, for CB-B2ES, polarity increased with a decreasing temperature, in contrast with the small decrease in polarity observed for analogous non-ethoxylated bilayers. This is consistent with increased hydration of the oxyethylene units in CB-B2ES bilayers at low temperatures. The periodic formation/breakdown and cooling-induced hydrophilicity of the CB-B2ES lamellar aggregates did not appear in the non-hybrid and/or non-ethoxylated surfactant systems. Therefore, the combination of two unsymmetrical tails, one containing oxyethylene units and the other containing cyanobiphenyl terminal tips, must play an important role promoting this unusual behavior.

Effect of Fluorocarbon and Hydrocarbon Chain Lengths in Hybrid Surfactants for Supercritical CO2.

Hybrid surfactants containing both fluorocarbon (FC) and hydrocarbon (HC) chains have recently been shown to solubilize water and form elongated reversed micelles in supercritical CO2. To clarify the most effective FC and HC chain lengths, the aggregation behavior and interfacial properties of hybrid surfactants FCm-HCn (FC length m/HC length n = 4/2, 4/4, 6/2, 6/4, 6/5, 6/6, and 6/8) were examined in W/CO2 mixtures as functions of pressure, temperature, and water-to-surfactant molar ratio (W0). The solubilizing power of hybrid surfactants for W/CO2 microemulsions was strongly affected by not only the FC length but also by that of the HC. Although the surfactants having short FC and/or HC tails (namely, m/n = 4/2, 4/4, and 6/2) did not dissolve in supercritical CO2 (even at ∼17 mM, ≤400 bar, temperature ≤ 75 °C, and W0 = 0-40), the other hybrid surfactants were able to yield transparent single-phase W/CO2 mixtures identified as microemulsions. The solubilizing power of FC6-HCm surfactants reached a maximum (W0 ∼ 80 at 45 °C and 350 bar) with a hydrocarbon length, m, of 4. The W0 value of 80 is the highest for a HC-FC hybrid surfactant, matching the highest value reported for a FC surfactant which contained more FC groups. High-pressure small-angle neutron scattering measurements from FCm-HCn/D2O/CO2 microemulsions were consistent with growth of the microemulsion droplets with increasing W0. In addition, not only spherical reversed micelles but also nonspherical assemblies (rodlike or ellipsoidal) were found for the systems with FC6-HCn (n = 4-6). At fixed surfactant concentration and W0 (17 mM and W0 = 20), the longest reversed micelles were obtained for FC6-HC6 where a mean aspect ratio of 6.3 was calculated for the aqueous cores.