Self-assembly Of Surfactant Molecules Research Articles

Isopentyltriphenylphosphonium bromideionic liquid as a newly effective corrosion inhibitor on metal-electrolyte interface in acidic medium: Experimental, surface morphological (SEM-EDX & AFM) and computational analysis

The behavior of mild steel (MS) corrosion in isopentyltriphenylphosphonium bromide (IPTPPB) as a green inhibitor into 0.5 M H2SO4 medium was examined by electrochemical techniques (galvanostatic (GP) and potentiostatic polarizations (PP), and electrochemical impedance spectroscopy (EIS)). Different concentrations of inhibitor were tried; maximum inhibition efficiency (99%) is obtained at 10−2 M IPTPPB in 0.5 M H2SO4. The temperature and adsorption effect was examined by the temperature kinetic study and simulation. The polarization technique explains the mixed type behavior of the inhibitor. The nature of inhibition of MS-IPTPPB was also studied by energy dispersive X-ray spectroscopic (EDXS) technique using surface analysis methods; scanning electron microscopy (SEM) and at atomic force microscopy (AFM). The formation of the monolayer by self-assembly of surfactant molecules at metal surfaces increases the corrosion inhibition ability. Experimental conclusions were found to be consistent with the semi-empirical AM1 method and molecular dynamics (MD) simulation theoretical calculations findings.

Replica exchange dissipative particle dynamics method on threadlike micellar aqueous solutions

The self-assembly of surfactant molecules can spontaneously result in a variety of micelle morphologies, such as spherical micelles, threadlike micelles, and vesicles, and it is therefore crucial to predict and control the self-assembly to achieve a helpful process in the fields of materials chemistry and engineering. A dissipative particle dynamics (DPD) method used in a coarse-grained molecular simulation is applied to simulate various self-assembling soft matter systems because it can handle greater length and time scales than a typical molecular dynamics simulation (MD). It should be noted that the thorough sampling of a system is not assured at low temperatures because of large complex systems with coarse-grained representations. In this article, we demonstrate that the replica exchange method (REM) is very effective for even a DPD in which the energy barrier is comparatively lower than that of a MD. A replica exchange on DPD (REDPD) simulation for threadlike micellar aqueous solutions was conducted, and the values of the potential energy and the mean aggregation number were compared. As a result, the correct values and a self-assembled structure within a low-temperature range can only be obtained through the REDPD.

Effect of the Crystallization Process of Surfactant Bilayer Lamellar Structures on the Elongation of High-Aspect-Ratio Gold Nanorods.

The growth mechanism of an "in-gel synthesis method", that is, the effects of composition and structure of the lamellar gel phase below the Krafft temperature of surfactant solutions on the growth of long gold nanorods, was investigated. We changed the alkyl chain length of surfactant molecules to investigate the effect of surfactant self-assembly on the elongation of gold nanorods systematically; eight mixed solutions of alkyltrimethylammonium bromide (C nTAB; n = 2-16; n = even) with C18TAB were used for investigation. The Krafft temperature, self-assembly of surfactant molecules, and the crystallization process of each mixture were observed by differential scanning calorimetry, wide-angle X-ray scattering, visual inspection, and small-angle X-ray scattering. Gold nanorods were synthesized in these eight surfactant mixtures. These observations demonstrated that when the surfactant Lβ phase sustains for a long time, the space of the water layer is also kept large enough for the seeds to take up Au ions bound to surfactant micelles. In this case, the seeds can form long nanorods between bilayers. We conclude that not only the stability of the lamellar gel phase but also co-existence of Au-ion carriers, that is, surfactant micelles, is essential for the elongation of long gold nanorods.

Effect of [Zr(α-PW11O39)2]10− Polyoxometalate on the Self-Assembly of Surfactant Molecules in Water Studied by Fluorescence and DOSY NMR Spectroscopy

The catalytic fragmentation of hydrophobic proteins by polyoxometalates (POMs) requires the presence of surfactants in order to increase the solubility of the protein. Depending on the nature of the surfactant, different effects on the kinetics of protein hydrolysis are observed. As the molecular interactions between the POMs and surfactants in solutions have been scarcely explored, in this study, the interaction between the catalytically active Keggin polyoxometalate [Zr(α-PW11O39)2]10− and four different surfactants—sodium dodecyl sulfate (SDS), dodecyldimethyl(3-sulfopropyl)ammonium (Zw3-12), dodecyldimethyl(3-sulfopropyl) ammonium (CHAPS), and polyethylene glycol tert-octylphenyl ether (TX-100)—have been studied in aqueous media. The effect of polyoxometalate on the self-assembly of surfactant molecules into micelles and on the critical micellar concentration (CMC) has been examined by fluorescence spectroscopy and diffusion ordered NMR spectroscopy (DOSY).

Molecular simulation of self-assembly structure and interfacial interaction for SDBS adsorption on graphene

Self-assembly of surfactant molecules on the graphene surface is of great importance for better preparation and application of graphene nanoparticles. Herein, classical molecular dynamics (MD) simulation has been performed to study the adsorption self-assembly of sodium dodecylbenzene sulfonate (SDBS) on nanosized graphene sheets. The effect of surface coverage on the self-assembly structure has been thoroughly investigated by quantifying various interfacial properties. In particular, we probed unique supramolecular morphology with SDBS adsorption on multilayer graphene nanosheets. Under higher surfactant concentration, multilayered micelles can be formed on the graphene surfaces. We also simulated the potential of mean force (PMF) between two nanoscale graphene sheets covered by SDBS surfactants in order to understand the interaction mechanism in the SDBS-based graphene dispersion and stabilization. This result verifies that the SDBS surfactants have ability to disperse and stabilize graphenes.

Production and Visualization of Vivid Streakline with the Self-Assembly of Surfactant Molecules

Production and Visualization of Vivid Streakline with the Self-Assembly of Surfactant Molecules

Production and Visualization of Vivid Streakline with the Self-Assembly of Surfactant Molecules

Aims: Streakline and its visualization and production techniques are one of important indices for fluid dynamics, civil engineering, material engineering, and so on. In chaotic or turbulent flow field where global mixing occurs, fluid trajectory exponentially expands in particular directions. Consequently, it is quite difficult to visualize streak as a “line” because experimental streak behaves as a “sheet” that has rounded surface. In the present study, to product and visualize a vivid and distinct streakline, a non-ionic surfactant was utilized. Study Design: Experimental study containing simulation.

Irreversible nanogel formation in surfactant solutions by microporous flow

Self-assembly of surfactant molecules into micelles of various shapes and forms has been extensively used to synthesize soft nanomaterials. Translucent solutions containing rod-like surfactant micelles can self-organize under flow to form viscoelastic gels. This flow-induced structure (FIS) formation has excited much fundamental research and pragmatic interest as a cost-effective manufacturing route for active nanomaterials. However, its practical impact has been very limited because all reported FIS transitions are reversible because the gel disintegrates soon after flow stoppage. We present a new microfluidics-assisted robust laminar-flow process, which allows for the generation of extension rates many orders of magnitude greater than is realizable in conventional devices, to produce purely flow-induced permanent nanogels. Cryogenic transmission electron microscopy imaging of the gel reveals a partially aligned micelle network. The critical flow rate for gel formation is consistent with the Turner-Cates fusion mechanism, proposed originally to explain reversible FIS formation in rod-like micelle solutions.

Thermodynamic Modeling of the Duality of Linear 1-Alcohols as Cosurfactants and Cosolvents in Self-Assembly of Surfactant Molecules

The effect of adding an alcohol to surfactant systems depends much on the alcohol chain length. Investigations on the effect of alcohols in micellar systems point out that medium-chain alcohols are appreciably incorporated in the micellar phase whereas short-chain alcohols are localized mainly in the aqueous phase. Nonetheless, penetration of the hydrocarbon chain of alcohols in the micellar shell has been experimentally observed for the entire homologous series of linear 1-alcohols. We present a thermodynamic model in which the alcohol molecules play two roles: cosurfactant and cosolvent. The cosurfactant effect of the alcohols is included by assuming that the alcohol molecules are nonionic surfactants. The cosolvent effect is modeled by accounting for the changes in the free energy to relocate the surfactant tail from the solvent to the aggregate core. The effects of short-chain alcohols in the macroscopic interfacial tension and dielectric constant of the solvent medium are also taken into account. For short-chain alcohols the partition coefficient of the alcohols between water and liquid hydrocarbons provides knowledge of the fraction of the molecules that participate in each function. Our proposed thermodynamic model improves the modeling of the effect of short- and medium-chain alcohols in self-assembly of molecules that are of increasing importance in modern scientific research and technological processes.

Diode-like ion-track asymmetric nanopores: Some alternative methods of fabrication

We present two fabrication methods which allow production of ion-track nanopore membranes with pronounced geometrical asymmetry and diode-like ionic conductivity. The asymmetry of the pores is provided by self-assembly of surfactant molecules at ion-track entrances on one side of the ion-irradiated polymer foil. On the other side of the membrane, the effect of surfactant is excluded using a pre-treatment with ultraviolet radiation or a surfactant-free etching solution. Highly tapered pore profiles are obtained and characterized using SEM and FESEM. In electrolyte solutions, the asymmetric pores thus fabricated exhibit a high rectification of electric current. The nanopores with a large angle aperture can be of interest for resistive-pulse technique applications and for the atomic beam projection nanolithography.

Directed Self-Assembly of Surfactants in Carbon Nanotube Materials

The self-assembly of surfactant molecules on crossing carbon nanotubes has been investigated using a bead-spring model and implicit solvent dissipative particle dynamics simulations. Adsorption is directed to the nanotube crossing by its higher hydrophobic potential which is due to the presence of two surfaces. As a consequence of the tendency of surfactant molecules to self-assemble into micelles, the adsorbed molecules form a "central aggregate" at the crossing, thus, confining the molecules to the immediate vicinity of the crossing. Adsorption on the remaining nanotube surface becomes significant only at higher surfactant concentrations, where the molecules self-assemble to hemimicelles which grow continuously to full micelles upon increase of the (bulk) surfactant concentration. Our results allow two conclusions for the rational design of nanostructured materials: (i) the size of the central aggregate can not be much larger than that of a bulk micelle and (ii) control of the adsorbed structures is conveniently possible via the (bulk) surfactant concentration.

Surfactant-controlled etching of ion track nanopores and its practical applications in membrane technology

The effect of surfactants on chemical development of ion tracks in polymers has been studied. It has been shown that surface-active agents added to an alkaline etching solution adsorb on the polymer surface at the pore entrances. This reduces the etch rate, which leads to the formation of pores tapered toward the surface. Self-assembly of surfactant molecules at the pore entrance creates a barrier for their penetration into the etched-out nanopores, whereas hydroxide ions diffuse freely. Due to this, the internal pore volume grows faster than the pore surface diameter. The ability to control pore shape is demonstrated with the fabrication of profiled nano- and micropores in polyethylene terephthalate, polycarbonate. Some earlier published data on small track-etched pores in polycarbonate (in particular, the pore diameter vs. etching time curves measured conductometrically) have been revised in light of the above findings. Adding surfactants to chemical etchants makes it possible to optimize the structure of track membranes, thus improving their retention and permeation properties. Asymmetric membranes with thin skin retention layers have been produced and their performance studied.

Fabrication and Characterization of Nanostructured Pd Hydride pH Microelectrodes

Novel pH microsensors were made by electrodepositing mesoporous Pd films onto Pt microdisks, electrochemically loading the films with hydrogen to form the alpha+beta Pd hydride phase, and then switching to the potentiometric mode to monitor pH. To create a nanostructure, the films were deposited within a molecular template formed by the self-assembly of surfactant molecules, a technique known as true liquid crystal templating. The films retain the micrometer size of the Pt microdisk but offer electroactive areas up to 900 times larger. Optimum hydrogen loading conditions were determined, and the mesoporous Pd microdisks were found to have excellent potentiometric properties. From pH 2 to 12, their potential was Nernstian, highly reproducible, very stable (+/-1.2 mV over 2 h), and without hysteresis. Their response time was better than 1 s. However, the presence of oxygen reduced their lifetime significantly, thereby requiring frequent reloading. These microelectrodes do not require calibration before and after measurements, a procedure normally essential for potentiometric pH microsensors. To our knowledge, these are the first results where nanostructured materials made by the true liquid crystal templating method have been used in the potentiometric mode; moreover, these are the first results demonstrating the application of nanostructured microdisks in the potentiometric mode.

Hygroscopic growth of self-assembled layered surfactant molecules at the interface between air and organic salts

We report here the self-assembly of surfactant molecules at the interface of air and the hygroscopic quaternary ammonium salt tetrabutylammonium acetate (TBAAc). Homogeneously dissolved surfactant molecules at 100 °C self-assemble upon contacting air due to high moisture adsorption by the organic salt when cooling down. Highly ordered lamellar phases with different lattice spacings have been observed when surfactants with various lengths of alkyl chains were used. C n TMAB/TBAAc systems showed all- trans conformation of interior methylene carbons and interdigited bilayers with an average CH 2 increment of 0.119 nm, while C n NH 2/TBAAc systems showed trans/gauche mixed conformations of interior methylene carbons and bilayers with an average CH 2 increment of 0.247 nm. C n NH 2s in C n NH 2/TBAAc formed bilayers through water-mediated intermolecular hydrogen bonds with a water layer thickness of 0.51–0.61 nm. In C n TAB/TBAAc, as the head group of C n TAB is bigger, the interdigited bilayer thickness ( d-spacing) is smaller, because the bigger head groups accommodate enough space for alkyl tails to come in between them.

Anomalous temperature dependence of surfactant self-assembly from aqueous solution.

The self-assembly of surfactant molecules from aqueous solutions exhibits anomalous and as yet unexplained temperature dependence. These effects include (a) a decrease in surfactant solubility, (b) an increase of the critical micelle concentration, and (c) increasing self-assembly on solid surfaces with increasing temperature near ambient temperature. These are the opposite of what one intuitively expects based on increasing molecular motion with temperature, and of what is observed for simpler fluids. Using a lattice gas theory that allows for inhomogeneity, hydrogen bonding, and micelle formation, we show conclusively that all of these phenomena arise from hydrogen bonding between water and the surfactant headgroups. While theory and experiment show very good qualitative agreement when such H bonding is included, its omission leads to complete reversal of the temperature dependence.

Hierarchically imprinted sorbents.

A double imprinting methodology was developed to synthesize novel materials with hierarchical structures. On the microporous level (1-3 A), metal ions served as template. On the mesoporous level (diameters of 25-40 A), micellar structures produced by self-assembly of surfactant molecules were used as templates. Removal of both metal ions and surfactant micelles resulted in the formation of imprints with different sizes within the silica matrix, each with a specific function. This research opens vast opportunities for the applications of ordered mesoporous materials in the area of molecular recognition such as separations, chemical sensors, and catalysts.

Formation and Structure of Self-Assembled Monolayers

The field of self-assembled monolayers (SAMs) has witnessed tremendous growth in synthetic sophistication and depth of characterization over the past 15 years.1 However, it is interesting to comment on the modest beginning and on important milestones. The field really began much earlier than is now recognized. In 1946 Zisman published the preparation of a monomolecular layer by adsorption (self-assembly) of a surfactant onto a clean metal surface.2 At that time, the potential of self-assembly was not recognized, and this publication initiated only a limited level of interest. Early work initiated in Kuhn’s laboratory at Gottingen, applying many years of experience in using chlorosilane derivative to hydrophobize glass, was followed by the more recent discovery, when Nuzzo and Allara showed that SAMs of alkanethiolates on gold can be prepared by adsorption of di-n-alkyl disulfides from dilute solutions.3 Getting away from the moisture-sensitive alkyl trichlorosilanes, as well as working with crystalline gold surfaces, were two important reasons for the success of these SAMs. Many self-assembly systems have since been investigated, but monolayers of alkanethiolates on gold are probably the most studied SAMs to date. The formation of monolayers by self-assembly of surfactant molecules at surfaces is one example of the general phenomena of self-assembly. In nature, self-assembly results in supermolecular hierarchical organizations of interlocking components that provides very complex systems.4 SAMs offer unique opportunities to increase fundamental understanding of self-organization, structure-property relationships, and interfacial phenomena. The ability to tailor both head and tail groups of the constituent molecules makes SAMs excellent systems for a more fundamental understanding of phenomena affected by competing intermolecular, molecular-substrates and molecule-solvent interactions like ordering and growth, wetting, adhesion, lubrication, and corrosion. That SAMs are well-defined and accessible makes them good model systems for studies of physical chemistry and statistical physics in two dimensions, and the crossover to three dimensions. SAMs provide the needed design flexibility, both at the individual molecular and at the material levels, and offer a vehicle for investigation of specific interactions at interfaces, and of the effect of increasing molecular complexity on the structure and stability of two-dimensional assemblies. These studies may eventually produce the design capabilities needed for assemblies of three-dimensional structures.5 However, this will require studies of more complex systems and the combination of what has been learned from SAMs with macromolecular science. The exponential growth in SAM research is a demonstration of the changes chemistry as a disciAbraham Ulman was born in Haifa, Israel, in 1946. He studied chemistry in the Bar-Ilan University in Ramat-Gan, Israel, and received his B.Sc. in 1969. He received his M.Sc. in phosphorus chemistry from Bar-Ilan University in 1971. After a brief period in industry, he moved to the Weizmann Institute in Rehovot, Israel, and received his Ph.D. in 1978 for work on heterosubstituted porphyrins. He then spent two years at Northwestern University in Evanston, IL, where his main interest was onedimensional organic conductors. In 1985 he joined the Corporate Research Laboratories of Eastman Kodak Company, in Rochester, NY, where his research interests were molecular design of materials for nonlinear optics and self-assembled monolayers. In 1994 he moved to Polytechnic University where he is the Alstadt-Lord-Mark Professor of Chemistry. His interests encompass self-assembled monolayers, surface engineering, polymers at interface, and surfaces phenomena. 1533 Chem. Rev. 1996, 96, 1533−1554

Molecular dynamics simulations of model oil/water/surfactant systems

Molecular dynamics simulations have been performed on amphiphilic molecules, oil and water to investigate surfactant behavior in water-like and oil-like solvents. Using a simple model for water, oil and surfactant molecules on a powerful parallel computer, we were able to simulate the adsorption of surfactants at the water/oil interface and the self-assembly of surfactant molecules into micelles. Simulations on various classes of surfactant molecules with different headgroup sizes and interactions show a strong dependence of the dynamics and morphology of surfactant aggregates on the surfactant structure. In the presence of an oil droplet, micelles induce the transfer of oil molecules from the oil droplet to the micelles by means of three mechanisms.