Nanoscopic microheterogeneities or pseudo-phase separations in non-conventional liquids

This article discusses new concepts in macroscopically monophasic colloidal systems, where entropy is a major driving force for very subtle interactions and structuring. First, we show how microemulsion-similar structures can be achieved with hydrotropes. These aggregates are less defined in structure and of shorter lifetime than classical micelles but still potentially useful microheterogeneities with internal interfaces. The other extreme case of strong interactions is given when cationic and anionic surfactants are mixed in equimolar ratios. It is well known that surfactants can be made more soluble when ethylene oxide groups are incorporated. This strategy is applied for such ‘catanionics’ to avoid surfactant precipitation. Finally, we consider the fact that ethylene oxide groups increase the size of the hydrophilic headgroups of carboxylates so that the geometrical constraints compel a direct spherical shape even in the absence of water. As a result, ‘water-free direct microemulsions’ with only charged surfactants and oil are conceivable.     

Synthesis of poly(n‐butyl acrylate) homopolymer and poly(styrene‐b‐n‐butyl acrylate‐b‐styrene) triblock copolymer via AGET emulsion ATRP using a cationic surfactant

Cationic emulsions of triblock copolymer particles comprising a poly(n‐butyl acrylate) (PⁿBA) central block and polystyrene (PS) outer blocks were synthesized by activator generated by electron transfer (AGET) atom transfer radical polymerization (ATRP). Difunctional ATRP initiator, ethylene bis(2‐bromoisobutyrate) (EBBiB), was used as initiator to synthesize the ABA type poly(styrene‐b‐n‐butyl acrylate‐b‐styrene) (PS‐PⁿBA‐PS) triblock copolymer. The effects of ligand and cationic surfactant on polymerizations were also discussed. Gel permeation chromatography (GPC) was used to characterize the molecular weight (M_n) and molecular weight distribution (MWD) of the resultant triblock copolymers. Particle size and particle size distribution of resulted latexes were characterized by dynamic light scattering (DLS). The resultant latexes showed good colloidal stability with average particle size around 100–300 nm in diameter. Glass transition temperature (T_g) of copolymers was studied by differential scanning calorimetry (DSC). © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 611–620     

Smart Soft‐Templating Synthesis of Hollow Mesoporous Bioactive Glass Spheres

Hollow bioactive glass spheres with mesoporous shells were prepared by using dual soft templates, a diblock co‐polymer poly(styrene‐b‐acrylic acid) (PS‐b‐PAA) and a cationic surfactant cetyltrimethylammonium bromide (CTAB). Hollow mesoporous bioactive glass (HMBG) spheres comprise the large hollow interior with vertical mesochannels in shell, which realize large uptake of drugs and their sustained release. The formation of hydroxyapatite layer on the surface of HMBG particles shows the clear evidence for promising application in bone regeneration.     

Morphological and Interaction Characteristics of Surface-Active Ionic Liquids and Palmitic Acid in Mixed Monolayers

A series of water soluble, surface-active ionic liquids (SAILs), namely, 1-alkyl-3-methyl imidazolium chlorides ([C_n-mim]Cl) and their mixtures with palmitic acid (PA) are investigated in Langmuir monolayers and Langmuir–Blodgett films. It is inferred from the surface pressure-area isotherms that C₁₆-mim-IL mixes non-ideally with PA and stabilizes the binary mixed films. In addition, the residence of mim-IL at the water surface is enhanced as a function of the increasing alkyl side chain length. Generally, the compressional moduli values decrease upon increasing the content of the mim-ILs over a wide range of compositions. Furthermore, film relaxation measurements indicate that the IL component is selectively excluded from the mixed films upon achieving a certain target pressure. Brewster angle microscope images demonstrate minimal changes on the PA domains in the presence of either C₄- and C₈-mim-ILs, whereas presence of the hexadecyl counterpart results in the formation of condensed sheets. Atomic force microscopy imaging of deposited films show the formation of propeller-like aggregates when C₈- or C₁₆-mim-IL is present in the mixed films.     

Spreading of Oil Droplets Containing Surfactants and Pesticides on Water Surface Based on the Marangoni Effect

Oil droplets containing surfactants and pesticides are expected to spread on a water surface, under the Marangoni effect, depending on the surfactant. Pesticides are transported into water through this phenomenon. A high-speed video camera was used to measure the movement of Marangoni ridges. Gas chromatography with an electron capture detector was used to analyze the concentration of the pesticide in water at different times. Oil droplets containing the surfactant and pesticide spread quickly on the water surface by Marangoni flow, forming an oil film and promoting emulsification of the oil–water interface, which enabled even transport of the pesticide into water, where it was then absorbed by weeds. Surfactants can decrease the surface tension of the water subphase after deposition, thereby enhancing the Marangoni effect in pesticide-containing oil droplets. The time and labor required for applying pesticides in rice fields can be greatly reduced by using the Marangoni effect to transport pesticides to the target.     

Liquid–liquid microextraction and spectrophotometric determination of anionic surfactants using Astra Phloxine FF

A novel and simple procedure for determination of anionic surfactants has been developed. The method is based on the reaction of sodium dodecyl sulphate (SDS) with Astra Phloxine FF reagent at pH 3–8, followed by liquid–liquid microextraction of the formed ion associate into an organic phase containing a mixture of carbon tetrachloride and dichloroethane (4:1, v/v) and subsequent UV-Vis detection at 555 nm. The calibration plot was linear in the range 0.006–0.29 mg L^?1 of SDS. The limit of detection (LOD), calculated based on 3s, is 0.002 mg L^?1. The method was applied to the determination of anionic surfactants in real wastewater samples.     

Fully printed flexible audio system on the basis of low‐voltage polymeric organic field effect transistors with three layer dielectric

Fully mass printed, flexible and truly polymeric organic field effect transistors consisting of a three layer dielectric made of CYTOP (low‐k), PVA (intermediate) and P(VDF‐TrFE‐CTFE)(high‐k) are introduced. Gravure‐, flexo‐and screen printing were selected as highly productive manufacturing technologies. These OFETs work at strongly reduced voltages and show high field effect mobility (µ = 0.2 cm²/Vs) and remarkable good bias stress stability at very high current density (50 µA/mm). Fully printed OFETs are used for the realization of ring oscillators working in the kHz regime at reduced supply voltage (10 V). In combination with printed fully polymeric piezoelectric loudspeakers, this work shows for the first time fully printed flexible audio systems. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1409–1415     

Synthesis and Design of Aggregation‐Induced Emission Surfactants: Direct Observation of Micelle Transitions and Microemulsion Droplets

The direct visualization of micelle transitions is a long‐standing challenge owing to the intractable aggregation‐caused quenching of light emission in the micelle solution. Herein, we report the synthesis of a surfactant with a tetraphenylethene (TPE) core and aggregation‐induced emission (AIE) characteristics. The transition processes of surfactant micelles and the microemulsion droplets (MEDs) formed by the surfactant with a TPE core were clearly visualized by a high‐contrast fluorescence imaging method. The fluorescence intensity of the MEDs decreased as the size of MEDs increased as a result of weakening of the restriction of intramolecular rotation (RIR). The results of this study deepen our understanding of micelle‐transition processes and provide solid evidence in favor of the hypothesis that the AIE phenomenon has its origin in the RIR of fluorophores in the aggregate state.     

Investigation of the surfactant type and concentration effect on the retention factors of glutathione and its analogues by micellar electrokinetic chromatography

In the present study, a micellar electrokinetic chromatographic method was used to determine the retention factors of hydrophilic monomeric and homodimeric forms of glutathione analogues. Ionic‐liquid‐based surfactant, 1‐tetradecyl‐3‐methylimidazolium chloride, as well as cetyltrimethylammonium bromide and phosphate buffer (pH 7.4) were employed in the experiments. Since the studied peptides possess a negative charge under physiological conditions, it is expected that the peptides interact with the oppositely charged 1‐tetradecyl‐3‐methylimidazolium chloride and cetyltrimethylammonium bromide micelles via hydrophobically assisted electrostatic forces. The dependence of the retention factor on the micellar concentration of 1‐tetradecyl‐3‐methylimidazolium chloride and cetyltrimethylammonium bromide is nonlinear and the obtained curves converge to a limiting value. The retention factor values of GSH analogues were in the range of 0.36–2.22 for glutathione analogues and –1.21 to 0.37 for glutathione when 1‐tetradecyl‐3‐methylimidazolium chloride was used. When cetyltrimethylammonium bromide was employed, the retention factor values were in the range of 0.27–2.17 for glutathione analogues and –1.22 to 0.06 for glutathione. If sodium dodecyl sulfate was used, the retention factor values of glutathione analogues with carnosine moiety were in the range of –1.54 to 0.38.     

Volatile surfactants: Characterization and areas of application

Amphiphilic aroma molecules, representatives of fragrance molecules, are introduced as dynamic volatile surfactants. Surface tension of their aqueous solutions proves to be a sensitive and revealing quantity, used for assessment of the adsorption-evaporation behavior both under equilibrium conditions and in regimes of no instantaneous equilibrium. Such volatile amphiphiles are characterized by fast adsorption from bulk solution at an air-water interface, on a timescale of tens of microseconds, and exhibit synergetic effect in mixtures with conventional micellar-forming surfactants. Their ability to evaporate from the interface on a time scale of minutes suggests their applications as “temporal” dynamic cosurfactants in technologies involving fast formation of new surfaces. Current challenges concern evaluation of specific material parameters of volatile aroma surfactants in order to enable their selection for targeted applications.