Surfactant Hexaethylene Glycol Monododecyl Ether Research Articles

Fluorocarbon Vapors Slow Down Coalescence in Foams

AbstractControlling the stability of liquid foams is of the utmost importance for a wide range of applications. For decades, fluorocarbon vapors have been added to the gas phase of foams to ensure long‐term stability against bubble coarsening. However, it is shown here for the first time that they also have an unexpected and pronounced effect on bubble coalescence. This effect is quantified in detail for foams stabilized by the nonionic surfactant hexaethylene glycol monododecyl ether (C12E6) at controlled fluorocarbon (perfluorohexane (C6F14)) concentrations, but it is observed for all investigated surfactants. Measuring surface tensions of the foaming solution with increasing fluorocarbon concentration, a synergy between the fluorocarbon and the surfactant is found which can be explained by a) the formation of mixed layers of both species at the gas/water interface at low fluorocarbon concentrations and b) the formation of a macroscopic fluorocarbon film if the gas phase is saturated with fluorocarbon vapor. The precise mechanism responsible for reducing coalescence, that is, film rupture, remains to be elucidated.

Emergence of Electric Fields at the Water-C12E6 Surfactant Interface.

We study the properties of the interface of water and the surfactant hexaethylene glycol monododecyl ether (C12E6) with a combination of heterodyne-detected vibrational sum frequency generation (HD-VSFG), Kelvin-probe measurements, and molecular dynamics (MD) simulations. We observe that the addition of the hydrogen-bonding surfactant C12E6, close to the critical micelle concentration (CMC), induces a drastic enhancement in the hydrogen bond strength of the water molecules close to the interface, as well as a flip in their net orientation. The mutual orientation of the water and C12E6 molecules leads to the emergence of a broad (∼3 nm) interface with a large electric field of ∼1 V/nm, as evidenced by the Kelvin-probe measurements and MD simulations. Our findings may open the door for the design of novel electric-field-tuned catalytic and light-harvesting systems anchored at the water-surfactant-air interface.

What happens when pesticides are solubilised in binary ionic/zwitterionic-nonionic mixed micelles?

HypothesisSurfactants have been widely used as adjuvants in agri-sprays to enhance the solubility of pesticides in foliar spray deposits and their mobility through leaf cuticles. Previously, we have characterised pesticide solubilisation in nonionic surfactant micelles, but what happens when pesticides become solubilised in anionic, cationic and zwitterionic and their mixtures with nonionic surfactants remain poorly characterised. ExperimentsTo facilitate characterisations by SANS and NMR, we used nonionic surfactant hexaethylene glycol monododecyl ether (C12E6), anionic sodium dodecylsulphate (SDS), cationic dodecyltrimethylammonium bromide (DTAB) and zwitterionic dodecylphosphocholine (C12PC) as model adjuvant systems to solubilise 3 pesticides, Cyprodinil (CP), Azoxystrobin (AZ) and Difenoconazole (DF), representing different structural features. The investigation focused on the influence of solubilisates in driving changes to the micellar nanostructures in the absence or presence of electrolytes. NMR and NOESY were applied to investigate the solubility and location of each pesticide in the micelles. SANS was used to reveal subtle changes to the micellar structures due to pesticide solubilisation with and without electrolytes. FindingsUnlike nonionic surfactants, the ionic and zwitterionic surfactant micellar structures remain unchanged upon pesticide solubilisation. Electrolytes slightly elongate the ionic surfactant micelles but have no effect on nonionic and zwitterionic surfactants. Pesticide solubilisation could alter the structures of the binary mixtures of ionic/zwitterionic and ionic/nonionic micelles by causing elongation, shell shrinkage and dehydration, with the exact alteration being determined by the molar ratio in the mixture.

What happens when pesticides are solubilized in nonionic surfactant micelles

Nonionic surfactants have been widely used in agri-sprays to enhance the solubility and mobility of pesticides, but what happens when pesticides become solubilized into surfactant micelles remains poorly characterized. To facilitate physical characterisations, we used the nonionic surfactant hexaethylene glycol monododecyl ether (C12E6) as a model system to solubilize 4 pesticides including Cyprodinil (CP), Diuron (DN), Azoxystrobin (AZ) and Difenoconazole (DF). The investigation focused on the influence of solubilizate and temperature in driving changes to the micellar nanostructures. Dynamic light scattering (DLS), cryogenic transmission electron microscopy (Cryo-TEM) and small-angle neutron scattering (SANS) measurements were used to reveal changes to the micellar structure before and after pesticide solubilisation. Nuclear magnetic resonance (NMR) was also applied to investigate the solubility and location of each pesticide in the micelles. Pesticides clearly altered the micellar structure, by increasing the aggregation number and micellar lengths, whilst shrinking and dehydrating the shells, leading to a consequent decrease in the dispersion cloud points. Increases in temperature affected micellar structures in a similar way. Thus, temperature increases and the solubilisation of pesticides can both make the surfactant effectively more hydrophobic, altering the micellar nanostructures and shifting the pesticide location within the micelles. These changes subsequently implicate how pesticides are delivered into plants through the natural wax films.

Structural Features of Reconstituted Cuticular Wax Films upon Interaction with Nonionic Surfactant C12E6.

The interaction of nonionic surfactant hexaethylene glycol monododecyl ether (C12E6) with a reconstituted cuticular wheat wax film has been investigated by spectroscopic ellipsometry and neutron reflection (NR) to help understand the role of the leaf wax barrier during pesticide uptake, focusing on the mimicry of the actions adjuvants impose on the physical integrity and transport of the cuticular wax films against surfactant concentration. As the C12E6 concentration was increased up to the critical micelle concentration (CMC = 0.067 mM), an increasing amount of surfactant mass was deposited onto the wax film. Alongside surface adsorption, C12E6 was also observed to penetrate the wax film, which is evident from the NR measurements using fully protonated and chain-deuterated surfactants. Furthermore, surfactant action upon the model wax film was found to be physically reversible below the CMC, as water rinsing could readily remove the adsorbed surfactant, leaving the wax film in its original state. Above the CMC, the detergency action of the surfactant became dominant, and a significant proportion of the wax film was removed, causing structural damage. The results thus reveal that both water and C12E6 could easily penetrate the wax film throughout the concentration range measured, indicating a clear pathway for the transport of active ingredients while the removal of the wax components above the CMC must have enhanced the transport process. As the partial removal of the wax film could also expose the underlying cutaneous substrate to the environment and undermine the plant's health, this study has a broad implication to the roles of surfactants in crop care.

Surfactant Adsorption onto Interfaces: Measuring the Surface Excess in Time

We propose a direct method to measure the equilibrium and dynamic surface properties of surfactant solutions with very low critical micellar concentrations (CMC) using a pendant drop tensiometer. We studied solutions of the nonionic surfactant hexaethylene glycol monododecyl ether (C(12)E(6)) and of the ionic surfactant hexadecyl trimethyl ammonium bromide (CTAB) with concentrated sodium bromide (NaBr). The variation of the surface tension as a function of surface concentration is obtained easily without the need for complex models and compares well with the result obtained using the Gibbs adsorption equation. The time-dependent surface concentration of each surfactant was also measured, and the adsorption process was found to be diffusion-controlled. The diffusion coefficients of the two surfactants can be extracted from the data and were found in very good agreement with literature values, further validating the method.

Effects of Temperature and Emulsifier Concentration on α-Tocopherol Distribution in a Stirred, Fluid, Emulsion. Thermodynamics of α-Tocopherol Transfer between the Oil and Interfacial Regions

The combined linear sweep voltammetry (LSV)/pseudophase kinetic model method was used to obtain the first estimates of the free energies, enthalpy, and entropies of transfer of alpha-tocopherol (TOC) between the oil and interfacial regions of fluid, opaque, emulsions of n-octane, acidic water, and the nonionic surfactant hexaethyleneglycol mono dodecyl ether (C12E6) from the temperature dependence of TOC's partition constant. Determining structure-reactivity relationships for chemical reactions in emulsions is difficult because traditional methods for monitoring reactions are unsuitable and because the partitioning of reactive components between the oil, interfacial, and aqueous regions of opaque emulsions are difficult to measure. The dependence of the observed rate constant, k(obs), for the reaction of an arenediazonium probe, 16-ArN2+, with TOC was determined as a function of C12E6 volume fraction. The pseudophase kinetic model was used to estimate the interfacial rate constant, k1, and the partition constants of antioxidants between the oil and interfacial, Po(I), regions in the emulsion from k(obs) versus phiI profiles. The thermodynamic parameters of transfer from the oil to the interfacial region at a series of temperatures were respectively obtained from the PoI values (deltaGT0,O-->I), by the van't Hoff method (deltaHT0,O-->I), and from the Gibbs equation (deltaST0,O-->I). The free energy of transfer is spontaneous, and a large positive entropy of transfer dominates a positive enthalpy of transfer, indicating that the TOC headgroup disrupts the structure of the interfacial region in its immediate vicinity upon transfer from n-octane. The methods described here are applicable to any bimolecular reaction in emulsions in which one of the reactants is restricted to the interfacial region and the rate of its reaction with a second component can be monitored electrochemically.

Investigation of the Soret effect in aqueous and non-aqueous mixtures by the thermal lens technique

In the present work we investigate the thermal diffusion behavior of three different binary mixtures with a thermal lens (TL) setup. In the setup used in this study we avoid the addition of a dye for systems, such as aqueous mixtures, with a weak absorption band at a wavelength of 980 nm. In some aqueous systems with a complex phase behavior the addition of dye significantly affects the apparent measured thermal diffusion properties. The studied systems are dimethylsulfoxide (DMSO) in water, the ionic liquid 1-ethyl-3-methylimidazolium ethylsulfate (EMIES) in butanol and a non-ionic surfactant hexaethylene glycol monododecyl ether (C(12)E(6)) in water. The Soret coefficients of the selected systems cover a range of two orders of magnitude. For DMSO in water with a very low Soret coefficient of the order of S(T) approximately 10(-3) K(-1) we find for a low DMSO content (c = 0.33) a reasonable agreement with previous measurements, while the weak thermal lens signal for the DMSO-rich mixture (c = 0.87) leads to 20% too large Soret coefficients with an uncertainty of more than 30%. Secondly we studied a liquid salt 1-ethyl-3-methylimidazolium ethylsulfate (EMIES) in butanol with a roughly ten times higher Soret coefficient of S(T) approximately 10(-2) K(-1). For this system we performed additional measurements with another experimental technique, the classical thermal diffusion forced Rayleigh scattering (TDFRS), which requires the addition of a small amount of dye to increase the absorption. In the entire investigated concentration range the results obtained with the TL and classical TDFRS technique agree within the error bars. As a third system we studied a non-ionic surfactant hexaethylene glycol monododecyl ether (C(12)E(6)) in water with a Soret coefficient of the order of S(T) approximately 10(-1) K(-1). For this system we find good agreement with previous measurements. We conclude that the TL technique is a reliable method for systems with a strong optical contrast and fairly large Soret coefficient of the order of S(T) approximately 10(-2) K(-1).

Kinetics and mechanism of the reaction between 4‐hexadecylbenzenediazonium ions and vitamin C in emulsions: further evidence of the formation of diazo ether intermediates in the course of the reaction

AbstractThe kinetics and mechanism of the reaction between hydrophobic 4‐hexadecylarenediazonium ions, 16‐ArN and vitamin C, VC, in a model emulsion prepared by mixing octane, acidic (HCl) water and the non‐ionic surfactant hexaethyleneglycol monododecyl ether, C12E6, were investigated. Because emulsions are opaque, linear sweep voltammetry, LSV, was employed to monitor the reaction. Voltammograms of 16‐ArN in emulsions show two reduction peaks as in aqueous systems. The half‐life for the spontaneous decomposition of 16‐ArN in the emulsion was estimated as t1/2 = 14.5 h at T = 25 °C. Upon addition of VC to the system, the first reduction peak of 16‐ArN disappears almost immediately and a new reduction peak is detected at Ep = −0.25 V. Electrochemical titration of 16‐ArN shows that the new peak corresponds to the formation of a 1:1 adduct. The iP(Ep = −0.25 V) values can be linearly correlated with [16‐ArN] and the observed rate constants, kobs, were determined by fitting the (ip, t) data to the integrated first order equation. The variation of kobs with [VC] follows a saturation kinetics profile, consistent with the formation of an intermediate in a pre‐equilibrium step. All the evidence is consistent with a reaction mechanism comprising two competitive pathways, the spontaneous DN + AN mechanism and the unimolecular decomposition of a transient diazo ether (DE) formed in a pre‐equilibrium step. The data allowed estimations of the interfacial rate constant for the reaction between 16‐ArN and VC− but did not allow the determination of the equilibrium constant for the DE formation. Copyright © 2008 John Wiley & Sons, Ltd.