Surface films of short fluorocarbon-hydrocarbon diblocks studied by molecular dynamics simulations: Spontaneous formation of elongated hemimicelles

Using grazing incidence small-angle X-ray scattering (GISAXS), and atomic force microscopy (AFM) it has been recently demonstrated that linear fluorocarbon-hydrocarbon diblocks (FnHm) self-assemble in water/air interfaces forming elongated and circular hemimicelles. Those structures have been observed for diblocks with at least eight fluorinated carbons. Based on the lack of a collapse pressure for F6H16, and due to the fact that no stable surface pressure values are reached under compression, it has been concluded that these molecules do not form stable monolayers. It has been also suggested that F6H16 and shorter diblocks desorb from the water surface under compression. It is not easy to accept that a significant concentration of so hydrophobic molecules can be stable in aqueous solution even when the employed experimental techniques were not able to clearly detect a well defined structure on the interface. In the present work the adsorption and arrangement of F6H16 and F6H10 at the water surface are studied by molecular dynamics (MD) simulations as a function of the available area per molecule. Starting from a random mixture, the spontaneous formation of elongated hemimicelles is observed for both systems when the area per molecule is higher than approximately 50 A(2). For intermediate areas two pseudo-phases, one rich in hydrocarbons and the other with higher fluorocarbon concentration, are formed. For the systems with less than approximately 30 A(2) available per molecule the formation of multilayers is observed. This is the first time that the dynamics and structure of perfluoroalkane (PFA) films, and in particular of hemimicelles on a liquid surface, are observed and characterized at atomic level.     

Effect of the Supporting Electrolyte on the Adsorption of Octanoic Acid at the Mercury/Electrolyte Interface

The adsorption and the changes in the interfacial composition of octanoic acid at the mercury/electrolyte interface was studied by measuring the differential capacitance at different concentrations of the supporting electrolyte, at various supporting electrolyte systems and at various temperatures. The adsorption was followed by means of capacity-potential curves in the short-term region and capacity-time transients in the long-term region at selected potentials, in all the potential ranges. A decrease of the capacitance with time was observed in most cases, followed either by a constant capacitance value or by its increase. In the short-term region, anion-surfactant complexes are formed, where the anions act as bridges between the perpendicularly oriented surfactant molecules. The larger is the negative charge of the anion, the more negative will be the charge of the anion-surfactant complex leading to a shift of the potential of maximal adsorption to more positive values. The formation of metastable condensed films is best when the hydration of the anion and its size are not too large. In the long-term region the observed increase of the capacity with time can be explained as an exchange of the metastable condensed film by a hemimicellar surface state. Here, the anions act as cores of the hemimicelles, and the hydrophilic acid groups of the amphiphiles contact the solution. Two contrary effects determine the formation of the hemimicelles. The greater is the specific adsorption of the anions, the larger is the formation of hemimicelles and the increase of the capacity. With an increase in the ability of the anions to break the water structure (lyotropic or Hofmeister series), the formation of hemimicelles will be decreased. Copyright 2000 Academic Press.     

Comparison between inhomogeneous adsorption of charged surfactants on air-water and on solid-water interfaces by self-consistent field theory

We use a realistic molecular model to study the interfacial behavior of hydrocarbon sulfate surfactants within a self-consistent field model and consider the adsorption both at the air-water interface and at a hydrophobic solid-water interface. We focus on the structural properties of the hemimicelles at the critical interface aggregation concentration (CIAC) for the air-water system and the critical surface aggregation concentration (CSAC) for the solid-water system. The major difference between the two systems is that the liquid interface is penetrable but the solid surface is intrinsically impenetrable for the molecular species. At the LG interface the hemimicelles have a lens shape with their centers of mass positioned slightly toward the aqueous side and feature an aspect ratio of approximately 2, with the long dimension parallel to the interface. Hemimicelle formation occurs below a critical (interfacial) area per molecule and above a critical surface pressure depending on tail length and ionic strength. Hemimicelles are not expected at air-water interfaces for a surfactant with a tail length ( t) lower than 15 CH2 units. In contrast, at a hydrophobic solid the formation of laterally inhomogeneous micelles even takes place for surfactants with the tail length as short as t = 12. This difference is attributed to the screening of the lateral interactions in the vapor phase. The shape of surface hemimicelles is caplike (or half-lens) with an aspect ratio lower than 2 and the long dimension parallel to the solid surface. The tail length, the ionic strength, the adsorption energies, and the surfactant concentration have an effect on the surface micelle properties such as the aggregation number and size and shape.     

Stacking of Self‐Assembled Surface Micelles in Ultrathin Films

Nonpolar fluorophilic/lipophilic tetrablock amphiphiles are investigated on the surface of water and on solid substrates using compression isotherms, Brewster angle microscopy, and atomic force microscopy. At low pressures, the tetrablocks form monolayers of closely packed surface hemimicelles. Further compression causes a 2D/3D transition. At the end of the plateau, half of the deposited material is expelled forming a second monolayer on top of the initially formed monolayer. Both layers of the films consist of surface micelles, thus providing the first example of spontaneous or compression‐driven stacking of self‐assembled nano‐objects.     

Occurrence, shape, and dimensions of large surface hemimicelles made of semifluorinated alkanes. Elongated versus circular Hemimicelles. Pit- and tip-centered hemimicelles

The formation of large (approximately 20-35 nm) surface hemimicelles in monolayers of semifluorinated alkanes, C(n)F(2)(n)(+1)C(m)H(2)(m)(+1) (FnHm), observed after transfer onto silicon wafers, is a general phenomenon. F6H16 and F8H14 exclusively form highly monodisperse circular hemimicelles, organized in a hexagonal array. The other FnHm investigated form both circular and elongated hemimicelles. The longer FnHm is, the larger the area fraction of elongated micelles; both the hydrocarbon block (H-block) and the fluorocarbon block (F-block) affect this area fraction. The length of the elongated micelles increases with the total length of the diblocks. The diameter of the circular micelles increases with the length of the H-block but, unexpectedly, not with that of the F-block. Model calculations account for these observations. Close examination of the circular micelles showed that they generally present a pit or a tip at their center. The width of the elongated micelles is comparable to the radius of the circular micelles, suggesting that the latter arise from a partition of elongated micelles, followed by coalescence of the edges of the resulting fragments. The elongated micelles become shorter and fewer when surface pressure increases, further suggesting a conversion of elongated into circular micelles. This conversion is reversible. The surface pressure-molecular area isotherms do not present any feature that forebears the existence of hemimicelles. The obtaining of stable surface patterns from simple, "nonpolar" molecular fluorocarbon/hydrocarbon diblocks opens a new approach for producing featured nanostructures from organic templates.     

Mixed hemimicelles solid-phase extraction based on cetyltrimethylammonium bromide-coated nano-magnets Fe3O4 for the determination of chlorophenols in environmental water samples coupled with liquid chromatography/spectrophotometry detection

Mixed hemimicelles solid-phase extraction (SPE) based on cetyltrimethylammonium bromide (CTAB)-coated nano-magnets Fe3O4 was investigated for the preconcentration of four chlorophenols (CPs) in environmental water samples prior to HPLC-spectrophotometry determination in this paper. By the rapid isolating (about 5 min) of Fe3O4 nanoparticles (NPs) through placing a Nd-Fe-B strong magnet on the bottom of beaker, the time-consuming preconcentration process of loading large volume sample in conversional SPE method with a column can be avoided. The unique properties of Fe3O4 NPs such as high surface area and strong magnetism were utilized adequately in the SPE process. This novel separation method produced a high preconcentration rate and factor. A comprehensive study of the adsorption conditions such as the Fe3O4 NPs zeta-potential, CTAB added amounts, pH value, standing time and maximal extraction volume was also presented. Under optimized conditions, four analytes of 2-chlorophenol (2-CP), 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (TCP) and pentachlorophenol (PCP) were quantitatively extracted. The method was then used to determine four CPs in five real environmental water samples. High concentration factors (700) were achieved for each of the analytes, with observed detection limits ranging between 0.11 and 0.15 microg L(-1). The accuracy of method was evaluated by recovery measurements on spiked samples. Good recovery results (83-98%) with satisfactory relative standard deviation (RSD) were achieved. It is important to note that satisfactory preconcentration factors and extraction recoveries for the four CPs were obtained with only a little amount of Fe3O4 NPs (0.1g) and CTAB (60 mg). To the best of our knowledge, this was the first time a mixed hemimicelles SPE method based on Fe3O4 NPs magnetic separation had been used for the pretreatment of environmental water samples.     

Stability of self-assembled hydrophobic surfactant layers in water

Using contact angle measurements, surface force balance experiments, and AFM imaging, we have investigated the process of self-assembly of surfactants onto mica and the subsequent stability of those layers in pure water. In the case of cetyltrimethylammonium bromide (CTAB), the stability of a monolayer when immersed in pure water is found to be dependent on initial immersion time in surfactant, which is likely to be caused by an increase in the proportion of ion-exchange to ion-pair adsorption when incubated in surfactant for longer periods of time. Infinite dilution of the surfactant solution before withdrawal of the sample is found to have little effect on the stability of the resulting layer in pure water. The nature of the counterion is found to affect dramatically the stability of a self-assembled surfactant monolayer: cetyltrimethylammonium fluoride (CTAF) forms a layer that is much more stable in water than CTAB, which is likely to be due to faster and more complete ion-exchange with the mica surface for CTAF. Surface force balance experiments show that when the hydrophobic monolayer is immersed in pure water it does not simply dissolve into the water; instead it rearranges, possibly to patches of bilayer or hemimicelles. The time scale of this rearrangement agrees well with the time scale of the change from a hydrophobic to more hydrophilic surface observed using contact angle measurements. AFM imaging has also in some cases shown an evolution from an even monolayer to patches of bilayer.     

Interaction of surfactants with hydrophobic surfaces in nanopores

Surfactant-induced wetting of hydrophobic nanopores is investigated. SDS micelles interact with the C18 layer on the nanopore walls with their hydrophobic tails, creating a charged wall lining with their head groups and inducing a breakthrough of the aqueous solution to wet the pores. The surface coverage of the surfactant molecules is evaluated electrophoretically. A surprising discovery is that pore wetting is achieved with 0.73 μmol/m(2) coverage of SDS surfactant, corresponding to only 18% of a monolayer on the walls of the nanopores. Clearly, the surfactant molecules cannot organize as a compact uninterrupted monolayer. Instead, formation of hemimicelles is thermodynamically favored. Modeling shows that, to be consistent with the experimental observations, the aggregation number of hemimicelles is lower than 25 and the size of hemimicelle is limited to a maximum radius of 11.7 ?. The hydrophobic tails of SDS thus penetrate into and intercalate with the C18 layer. The insight gained in the C18-surfactant interactions is essential in the surfactant-induced solubilization of hydrophobic nanoporous particles. The results have bearing on the understanding of the nature of hydrophobic interactions.     

烷基硫酸钠在二氧化钛上的吸附研究

表面活性剂在氧化物表面上的吸附,因其在浮选中的重要作用而被广泛研究。但迄今为上的工作多是关于表面活性离子在电性相反的氧化物表面上,例如阳离子表面活性剂在带负电的氧化物表面上的吸附,而对电性相同的表面活性离子的吸附则很少涉及,虽然许多实际问题中遇到的是后一种情形。本工作研究了烷基硫酸钠在带负电的TiO₂表面上的吸附,根据吸附与电泳的实验结果计算了吸附自由能,并提出了可能的吸附机理。     

Polystyrene nanorod formation in <Emphasis Type="Italic">C</Emphasis><Subscript>12</Subscript><Emphasis Type="Italic">E</Emphasis><Subscript>5</Subscript> hemimicelle thin film templates

This paper reports the synthesis and characterization of polystyrene nanorods in hemicylindrical hemimicelles of a nonionic polyoxyethylene surfactant, C ₁₂ E ₅, on graphite. The surface structure is characterized by atomic force microscopy (AFM), Fourier transform infrared spectroscopy, and contact angle goniometry. Uniformly aligned polystyrene nanorods are captured by AFM. The nanorod dimensions are studied as a function of the reaction time and styrene monomer concentration. The template synthesis using self-assembled surfactant surface aggregates promises to create functional and stable nanostructures for optoelectronics and surface engineering.     

The surface properties of tetradecyltrimethylammonium bromide observed by capillary electrophoresis

The electroosmotic flow (EOF) is measured as a function of tetradecyltrimethylammonium bromide (TTAB) concentration and is shown to have distinct zones that are pH dependent. The data is correlated with previously proposed surface structures ranging from unimolecular adsorption to hemimicelles and micelles of TTAB adsorbed on the hydrated fused silica. A plot of the TTAB concentration at zero EOF versus pH shows that the zero point of charge (zpc) is pH dependent and that a linear extrapolation of the data intercepts close to the pH value for the zpc of a fused-silica surface. This shows that different surface properties at different pH values at any given TTAB concentration are generally dealt with. Therefore, these pH-dependent structures of the fused-silica surface have to be taken into account while studying these phenomena.     

离子型表面活性剂自组装体系在化学中的应用

本文介绍了离子型表面活性剂在氧化物表面自组装体系的原理及特点，离子型表面活性剂分子从溶液中自发地吸附到氧化物表面形成单分子胶束、双分子胶束和混合胶束，该体系对许多疏水性有机化合物以及经螯合有机基团的金属离子具有很强的吸附富集作用，本文根据不同自组装体系的结构分类详述了它们在分析化学和环境化学中应用研究，并且展望了该技术的应用前景。     

Mixed Hemimicelles Solid phase Extraction of Atrazine and Simazine from Environmental Water Samples Using Alumina-Coated Magnetite Composite Material

Journal of Analytical Chemistry - A sensitive and selective mixed hemimicelles solid phase extraction magnetic material based on sodium dodecyl sulfate-coated magnetite (Fe3O4)/alumina (Al2O3) is...     

Study of the influence of water matrix components on admicellar sorbents

Hemimicelle-based and/or admicelle-based solid-phase extraction (SPE) has recently been proved to be a fruitful strategy for the extraction and concentration of a wide variety of organic pollutants. This research focus on the effect of river and wastewater matrix components on the adsorption of sodium dodecyl sulfate (SDS) onto alumina, which is the most-used sorbent in hemimicelle-based and/or admicelle-based SPE, and we discuss the analytical consequences of the modifications observed. The effect of electrolytes (0.1 M NaCl), precipitating agents (127 and 333 mg L⁻¹ CaCl₂) and major organic components in wastewater (19.8 mg L⁻¹ carbohydrates, proteins and fats and 10 mg L⁻¹ linear alkylbenzene sulfonates (LAS) and rivers (8 mg L⁻¹ humic acid) on the SDS adsorption isotherm was investigated. Also, the global effect of matrix components was assessed using a river sample. Three types of sorbents were considered (hemimicelles, mixed hemimicelles/admicelles and admicelles). Electrolytes were found to compete with surfactant molecules for charge surface sites in the early part of the hemimicellar region; precipitating agents yield insoluble salts with the aqueous surfactant in equilibrium with admicelle-based sorbents; and organic matter did not have any influence at all. The matrix component concentrations investigated were above the usual range present in rivers and wastewater, which makes this study applicable to a wide number of environmental water samples. From the results obtained, simple rules were established to prevent and detect matrix-induced surfactant adsorption modifications, which permits us to know, a priori, the suitability of these sorbents for a specific application and allows the development of more straightforward and robust methods.     

The adsorption of alkylpyridinium chlorides and their effect on the interfacial behavior of quartz

This research was directed at understanding cationic surfactant adsorption phenomena on wet-ground natural quartz, mainly with dodecylpyridinium chloride as the model surfactant. How these surfactant ions adsorb at the interface was delineated through measurements of adsorption isotherms, zeta potentials, suspension stability, contact angles, induction times, and flotation response. Hydrocarbon chain association of adsorbed surfactant ions (or self-association) leads to four distinct adsorption regions as the concentration of surfactant is increased in solution. The same four regions manifest themselves in the behavior of all of the interfacial processes studied. At low concentrations, adsorption is controlled primarily by electrostatic interactions, but when the adsorbed surfactant ions begin to associate into hemimicelles at the surface, hydrophobic chain interactions control the adsorption process. The results of experiments with alkylpyridinium chlorides of 12, 14 and 16 carbon atoms can be normalized in terms of their CMCs, which clearly show that surface aggregation phenomena are driven by the same hydrophobic interactions that lead to micelle formation in bulk solution.     

Preparation of silica-magnetite nanoparticle mixed hemimicelle sorbents for extraction of several typical phenolic compounds from environmental water samples

A novel type of superparamagnetic silica-coated (Fe3O4/SiO2 core/shell) magnetite nanoparticle modified by surfactants has been successfully synthesized and was applied as an effective sorbent material for the pre-concentration of several typical phenolic compounds (bisphenol A (BPA), 4-tert-octylphenol (4-OP) and 4-n-nonylphenol (4-NP)) from environmental water samples. Compared with pure magnetic particles, a thin and dense silica layer would protect the iron oxide core from leaching out in acidic conditions. In order to enhance their adsorptive tendency towards organic compounds, cetylpyridinium chloride (CPC) or cetyltrimethylammonium bromide (CTAB) were added, which adsorbed on the surface of the Fe3O4/SiO2 nanoparticles (Fe3O4/SiO2 NPs) and formed mixed hemimicelles. Main factors affecting the adsolubilization of analytes were optimized and comparative study on the use of CPC and CTAB-coated Fe3O4/SiO2 NPs mixed hemimicelles-based SPE was also carried out. CPC-coated Fe3O4/SiO2 NPs system was selected due to lower elution volume required and more effective adsorption of the target compounds. Under selected conditions, concentration factor of 1600 was achieved by using this method to extract 800 mL of different environmental water samples. The detection limits obtained for BPA, 4-OP and 4-NP with HPLC-FLD were 7, 14, and 20 ng/L, respectively.     

Multifunctional sorbents for the extraction of pesticide multiresidues from natural waters

In this work multifunctional sorbents, based on surfactant-coated mineral oxides, are assessed for the simultaneous extraction/preconcentration of pesticide multiresidues from aqueous environmental samples. Seventeen pesticides, representative of all the common groups (triazines, phenylureas, carbamates, azols, anilides, chloroacetanilides, organophosphorous, phenoxyacids, aryloxy acids and phenols), are selected for this study. The sorbents assessed are pure sodium dodecyl sulphate (SDS) and mixed tetrabutylammonium (TBA)-SDS hemimicelles and/or admicelles adsorbed onto alumina. Because of their multifunctional character, these sorbents provide different retention mechanisms (i.e. hydrophobic, ionic and/or π-cation interactions), which highly contribute to the efficient retention of pesticides with different polarities and acidities (bases, neutrals and acids). In addition, the low volume of eluent required for complete elution of analytes (typically 1-2 mL) avoided the need of using time-consuming and tedious evaporation steps that generally are needed when cross-linked polymeric resins or carbon materials are used as sorbents. The performance of two sorbents, i.e. SDS and TBA-SDS mixed hemimicelles/admicelles, for the admicellar solid-phase extraction (ASPE) of pesticide multiresidue was comparatively investigated. The latter was selected on the basis of the higher breakthrough volumes permitted, the lower volume of eluent required and the higher sample and eluent flow rates allowed. The proposed ASPE/LC/UV approach provided detection limits lower than 100 ng L⁻¹ for the determination of the 17 pesticides tested. Recoveries from spiked (at the ng L⁻¹ level) river and underground water samples was quantitative for most of the pesticides tested.     

Cetyltrimethylammonium bromide-coated titanate nanotubes for solid-phase extraction of phthalate esters from natural waters prior to high-performance liquid chromatography analysis

As a novel nanomaterial, titanate nanotube has attracted considerable attention recently. However, most of the research work is focused on the preparation of this nanomaterial, and there is lack of information about its application in the fields of environmental monitoring and analytical chemistry. The purpose of our study is to investigate the feasibility of titanate nanotubes as an adsorbent for solid-phase extraction of several phthalate esters. The titanate nanotubes in this study were prepared by alkaline hydrothermal method. The cationic surfactant cetyltrimethylammonium bromide (CTAB)-titanate nanotube system was adopted based on hemimicelles/admicelles formed on the mineral oxide surface. It was shown in the batch experiment that the highest adsorption of phthalate esters onto the CTAB-titania and -titanate nanotube system occurred when the CTAB was varied from 100 to 200mgg(-1) titania or 80 to 300mgg(-1) titanate nanotube separately. According to the fluorescent spectra of a molecular probe, N-phenyl-1-naphthylamine, and the binding constant of solute in CTAB admicelles, the CTAB-titanate nanotube admicelles was more hydrophobic than CTAB-titania admicelles. Consequently, CTAB-titanate nanotube admicelles system was suitable for concentrating phthalates esters in water. An admicelle column was prepared with 100mg of titanate nanotubes by passing through 100mgg(-1) titanate nanotube of CTAB. And excellent collection yields were obtained for all the analytes when the sample volume was up to 1000mL. Under the optimal conditions, the detection limits found for di-n-propyl-phthalate, di-n-butyl-phthalate, di-cyclohexyl-phthalate, and di-n-octyl-phthalate were 39, 19, 35 and 20ngL(-1), respectively. The developed method was successfully applied to the analysis of several real water samples and satisfactory recoveries were achieved. All the results indicated the application potential of titanate nanotubes as solid-phase extraction adsorbents to pre-treat water samples.     

Lateral and vertical nanophase separation in Langmuir-Blodgett films of phospholipids and semifluorinated alkanes

It has recently been found that monodisperse surface micelles (hemimicelles) were formed in Langmuir monolayers of the semifluorinated alkane C8F17C16H33 (F8H16) after transfer onto silicon wafers. Grazing incidence X-ray diffraction studies have demonstrated that compression of mixed Langmuir monolayers made from combinations of dipalmitoyl phosphatidylethanolamine (DPPE) and diblock F8H16 in various molar ratios resulted in the complete expulsion of the diblock molecule at high surface pressure. F8H16 then formed a second layer on top of a DPPE-only monolayer, demonstrating a novel type of reversible, pressure-induced, vertical phase separation. Using atomic force microscopy and X-ray reflectivity, we show now that mixed DPPE/F8H16 (1:1.3) Langmuir-Blodgett films transferred onto silicon wafers below 10 mN m(-1) are laterally phase separated and consist of domains of F8H16 surface micelles in coexistence with a monolayer of DPPE. The density of the network of F8H16 surface micelles increases when the surface pressure of transfer increases. Around 10 mN m(-1), the F8H16 surface micelles start to glide on the DPPE monolayer, progressively overlying it, until total coverage is achieved.     

Self-association and reverse hemimicelle formation at solid–water interfaces in dilute surfactant solutions

Using monodisperse anatase and hematite particles, such classical techniques as colloid stability, ζ potential and wettability measurements along with fluorescence spectroscopy show that anionic alkyl sulfate and sulfonate surfactants first associate into hemimicelles at the interface and cause the particles to begin to coagulate and to become hydrophobic. Maximum coagulation and hydrophobicity occur under conditions where the ζ potential is zero. At higher surfactant concentrations, the particles redisperse and regain their hydrophilicity. Upon reversal of the ζ potential, the adsorbed surfactant ions appear to form hemimicelles with reverse orientation or bilayers, at surfactant concentrations significantly lower than the critical micelle concentration. The results of these experiments correlate well with spectroscopic and adsorption measurements.