The dynamic nature of natural and fatty acid modified calcite surfaces.

Calcium carbonate, particularly in the form of calcite, is an abundant mineral widely used in both human-made products and biological systems. The calcite surface possesses a high surface energy, making it susceptible to the adsorption of organic contaminants. Moreover, the surface is also reactive towards a range of chemicals, including water. Consequently, studying and maintaining a clean and stable calcite surface is only possible under ultrahigh vacuum conditions and for limited amounts of time. When exposed to air or solution, the calcite surface undergoes rapid transformations, demanding a comprehensive understanding of the properties of calcite surfaces in different environments. Similarly, attention must also be directed towards the kinetics of changes, whether induced by fluctuating environments or at constant condition. All these aspects are encompassed in the expression "dynamic nature", and are of crucial importance in the context of the diverse applications of calcite. In many instances, the calcite surface is modified by adsorption of fatty acids to impart a desired nonpolar character. Although the binding between carboxylic acid groups and calcite surfaces is strong, the fatty acid layer used for surface modification undergoes significant alterations when exposed to water vapour and liquid water droplets. Therefore, it is also crucial to understand the dynamic nature of the adsorbed layer. This review article provides a comprehensive overview of the current understanding of both the dynamics of the calcite surface as well as when modified by fatty acid surface treatments.

Calcite Surfaces Modified with Carboxylic Acids (C2 to C18): Layer Organization, Wettability, Stability, and Molecular Structural Properties.

A fundamental understanding of the interactions between mineral surfaces and amphiphilic surface modification agents is needed for better control over the production and uses of mineral fillers. Here, we controlled the carboxylic acid layer formation conditions on calcite surfaces with high precision via vapor deposition. The properties of the resulting carboxylic acid layers were analyzed using surface-sensitive techniques, such as atomic force microscopy (AFM), contact angle measurements, angle resolved X-ray photoelectron spectroscopy (XPS), and vibrational sum-frequency spectroscopy. A low wettability was achieved with long hydrocarbon chain carboxylic acids such as stearic acid. The stearic acid layer formed by vapor deposition is initially patchy, but with increasing vapor exposure time, the patches grow and condense into a homogeneous layer with a thickness close to that expected for a monolayer as evaluated by AFM and XPS. The build-up process of the layer occurs more rapidly at higher temperatures due to the higher vapor pressure. The stability of the deposited fatty acid layer in the presence of a water droplet increases with the chain length and packing density in the adsorbed layer. Vibrational sum frequency spectroscopy data demonstrate that the stearic acid monolayers on calcite have their alkyl chains in an all-trans conformation and are anisotropically distributed on the plane of the surface, forming epitaxial monolayers. Vibrational spectra also show that the stearic acid molecules interact with the calcite surface through the carboxylic acid headgroup in both its protonated and deprotonated forms. The results presented provide new molecular insights into the properties of adsorbed carboxylic acid layers on calcite.

Silica Surface Charge Enhancement at Elevated Temperatures Revealed by Interfacial Water Signals.

The structure of water adjacent to silica is sensitive to the degree of deprotonation of surface silanol groups. As a result, close inspection of signals originating from these water molecules can be used to reveal the surface charge density. We have used nonlinear vibrational spectroscopy of the water O-H stretching band over a temperature range of 10-75 °C to account for the increase in surface potential from deprotonation. We demonstrate that the behavior at the silica surface is a balance between increasing surface charge and a decreasing contribution of water molecules aligned by the surface charge. Together with a model that accounts for two different types of silanol sites, we use our data to report the changes in enthalpy and entropy for deprotonation at each site. This is the first experimental determination of these thermodynamic parameters for hydrated silanol groups at the silica surface, critical to a wide range of geochemical and technological applications.

Cryoporometry in Femtoliter Volumes by Confocal Raman Spectroscopy.

The properties of porous material are largely dependent on the size, shape, and connectivity of the pores. Here, we present a method based on confocal Raman spectroscopy to quantify porosity using a cryoporometric approach. We show that the phase transition of water imbibed in porous silica can be accurately determined using two different, but complementary methodologies. The first one relies on integrating the temperature-dependent spectral intensities across the whole OH (H2O) or OD (D2O) stretching region. The second, more quantitative approach, deconvolutes the spectral contributions within the pores in terms of liquid and solid fractions. The results show the expected reciprocal dependence of the average phase transition point with pore size, as well as the typical hysteresis between the freezing and melting transitions. One of the key advantages of the confocal Raman approach is its high spatial resolution, with sampling volumes starting from just a few femtoliters, opening the possibility of mapping the structure in heterogeneous porous materials.

Molecular insight into carboxylic acid-alkali metal cations interactions: reversed affinities and ion-pair formation revealed by non-linear optics and simulations.

Specific interactions between the carboxylic acid moiety and the monovalent salts CsCl, NaCl, and LiCl, have been investigated in Langmuir monolayers using vibrational sum frequency spectroscopy (VSFS) and complemented with coarse grained and all-atom molecular dynamics simulations. By exploiting VSFS's intrinsic surface specificity, an emphasis was made on targeting headgroup vibrations of both its charged and uncharged forms as well as water molecules in the interfacial layer. The degree of deprotonation of the monolayer as a function of cation concentration and pH was experimentally determined and theoretically rationalized. Starting from 100 mM, the surface charge was overestimated by the Gouy-Chapman model and varied depending on the identity of the cation, highlighting the appearance of ion specific effects. Agreement could be found using a modified Poisson-Boltzmann model that takes into account steric effects, with a fitted effective ion-size compatible with the hydrated ion diameters. The relative affinity of the cations to the carboxylic acid moiety was pH dependent: at pH 4.5 they arranged in the order Cs+ > Na+ > Li+, but fully reversed (Li+ > Na+ > Cs+) at pH 9. Simulations yielded microscopic insight into the origin of this behavior, with the cations showing contrasting interaction preferences for either the uncharged carboxylic acid or the charged carboxylate. Sum frequency spectra also provided evidence that all cations remained hydrated when interacting with the charged headgroup, forming solvent-separated or solvent-shared ion pairs. However, for the specific case of 1 M Li+ at pH 9, contact ion pairs were formed. Finally, the remarkable effect of trace metal multivalent cations in the interpretation of experiments is briefly discussed. The results provide exciting new insights into the complex interactions of alkali metal cations with the biophysically relevant carboxylic acid moiety.

Water at Interfaces.

The interfaces of neat water and aqueous solutions play a prominent role in many technological processes and in the environment. Examples of aqueous interfaces are ultrathin water films that cover most hydrophilic surfaces under ambient relative humidities, the liquid/solid interface which drives many electrochemical reactions, and the liquid/vapor interface, which governs the uptake and release of trace gases by the oceans and cloud droplets. In this article we review some of the recent experimental and theoretical advances in our knowledge of the properties of aqueous interfaces and discuss open questions and gaps in our understanding.

The elusive silica/water interface: isolated silanols under water as revealed by vibrational sum frequency spectroscopy.

It has been long recognized that the surface chemistry of silica, and in particular the type and relative amount of surface bound silanol groups, plays a critical role in many of the properties associated with the material, where a typical example is the discrepant adsorption behavior observed depending on the pretreatment history of the surface. However, in spite of its importance, the direct probing of specific surface silanol groups under water has been hampered by instrumental limitations. Here we make use of vibrational sum frequency spectroscopy (VSFS) to first, identify under water the OH stretch of isolated surface silanols, and second, explore its acid/base behavior and dependence on the surface pretreatment method. The properties of other types of silanol groups (i.e. hydrogen bonded/geminal) are also inferred from the data. The ability to directly probe these functional groups under water represents a crucial step to further improving our understanding of this widely used mineral oxide.

Temperature-Dependent Deicing Properties of Electrostatically Anchored Branched Brush Layers of Poly(ethylene oxide).

The hydration water of hydrophilic polymers freezes at subzero temperatures. The adsorption of such polymers will result in a hydrophilic surface layer that strongly binds water. Provided this interfacial hydration water remains liquidlike at subzero temperatures, its presence could possibly reduce ice adhesion, in particular, if the liquidlike layer is thicker than or comparable to the surface roughness. To explore this idea, a diblock copolymer, having one branched bottle-brush block of poly(ethylene oxide) and one linear cationic block, was electrostatically anchored on flat silica surfaces. The shear ice adhesion strength on such polymer-coated surfaces was investigated down to -25 °C using a homebuilt device. In addition, the temperature dependence of the ice adhesion on surfaces coated with only the cationic block, only the branched bottle-brush block, and with linear poly(ethylene oxide) was investigated. Significant ice adhesion reduction, in particular, at temperatures above -15 °C, was observed on silica surfaces coated with the electrostatically anchored diblock copolymer. Differential scanning calorimetry measurements on bulk polymer solutions demonstrate different thermal transitions of water interacting with branched and linear poly(ethylene oxide) (with hydration water melting points of about -18 and -10 °C, respectively). This difference is consistent with the low shear ice adhesion strength measured on surfaces carrying branched bottle-brush structured poly(ethylene oxide) at -10 °C, whereas no significant adhesion reduction was obtained with linear poly(ethylene oxide) at this temperature. We propose a lubrication effect of the hydration water bound to the branched bottle-brush structured poly(ethylene oxide), which, in the bulk, does not freeze until -18 °C.

The premolten layer of ice next to a hydrophilic solid surface: correlating adhesion with molecular properties.

In order to establish the potential correlation between the macroscopic ice adhesion and the molecular properties of the premolten layer (PML), the adhesion strength between ice and hydrophilic silica has been measured as a function of temperature. In addition, temperature-dependent molecular properties have been determined using techniques that are sensitive to different aspects of the PML, specifically total internal reflection (TIR) Raman, vibrational sum frequency (VSFS) and NMR spectroscopies. The ice shear adhesion strength was observed to increase linearly with decreasing temperature until -25 °C, where a plateau marked the adhesive strength having reached the cohesive strength of ice. Interestingly, at temperatures higher than -20 °C the ice samples slid on smooth (Ra < 0.4 nm) silica surfaces. This sliding behavior was not observed on rougher silica surfaces (Ra ∼ 6 nm). By varying the penetration depth of the evanescent field, TIR Raman was used to establish an upper limit to the thickness of the PML in contact with silica (<3 nm even at -0.3 K below the bulk melting temperature). Additional quantitative determination of the temperature-dependent thickness of the PML was obtained from 2H NMR measurements in mesoporous silica particles. Finally, the inherently surface specific technique, VSFS, which probed changes in the hydrogen bond environment, indicated at approximately -25 °C the onset of PML, followed by a marked structural change occurring just a fraction of a degree below the melting temperature. Jointly, the experimental approaches link, strongly and consistently, ice adhesion to the PML properties. Specifically, it is inferred that the premolten layer facilitates sliding and contributes to the observed friction behavior, provided its thickness is comparable to the surface roughness of the underlying silica substrate.

Surface grafted chitosan gels. Part I. Molecular insight into the formation of chitosan and poly(acrylic acid) multilayers.

Composite polyelectrolyte multilayers of chitosan and low molecular weight poly(acrylic acid) (PAA) have been assembled by sequential adsorption as a first step toward building a surface anchored chitosan gel. Silane chemistry was used to graft the first chitosan layer to prevent film detachment and decomposition. The assembly process is characterized by nonlinear growth behavior, with different adsorption kinetics for chitosan and PAA. In situ analysis of the multilayer by means of surface sensitive total internal reflection Raman (TIRR) spectroscopy, combined with target factor analysis of the spectra, provided information regarding composition, including water content, and ionization state of weak acidic and basic groups present in the thin composite film. Low molecular weight PAA, mainly in its protonated form, diffuses into and out of the composite film during adsorption and rinsing steps. The higher molecular weight chitosan shows a similar behavior, although to a much lower extent. Our data demonstrate that the charged monomeric units of chitosan are mainly compensated by carboxylate ions from PAA. Furthermore, the morphology and mechanical properties of the multilayers were investigated in situ using atomic force microscopy operating in PeakForce tapping mode. The multilayer consists of islands that grow in lateral dimension and height during the build-up process, leading to close to exponentially increasing roughness with deposition number. Both diffusion in and out of at least one of the two components (PAA) and the island-like morphology contribute to the nonlinear growth of chitosan/PAA multilayers.

Surface grafted chitosan gels. Part II. Gel formation and characterization.

Responsive biomaterial hydrogels attract significant attention due to their biocompatibility and degradability. In order to make chitosan based gels, we first graft one layer of chitosan to silica, and then build a chitosan/poly(acrylic acid) multilayer using the layer-by-layer approach. After cross-linking the chitosan present in the polyelectrolyte multilayer, poly(acrylic acid) is partly removed by exposing the multilayer structure to a concentrated carbonate buffer solution at a high pH, leaving a surface-grafted cross-linked gel. Chemical cross-linking enhances the gel stability against detachment and decomposition. The chemical reaction between gluteraldehyde, the cross-linking agent, and chitosan was followed in situ using total internal reflection Raman (TIRR) spectroscopy, which provided a molecular insight into the complex reaction mechanism, as well as the means to quantify the cross-linking density. The amount of poly(acrylic acid) trapped inside the surface grafted films was found to decrease with decreasing cross-linking density, as confirmed in situ using TIRR, and ex situ by Fourier transform infrared (FTIR) measurements on dried films. The responsiveness of the chitosan-based gels with respect to pH changes was probed by quartz crystal microbalance with dissipation (QCM-D) and TIRR. Highly cross-linked gels show a small and fully reversible behavior when the solution pH is switched between pH 2.7 and 5.7. In contrast, low cross-linked gels are more responsive to pH changes, but the response is fully reversible only after the first exposure to the acidic solution, once an internal restructuring of the gel has taken place. Two distinct pKa's for both chitosan and poly(acrylic acid), were determined for the cross-linked structure using TIRR. They are associated with populations of chargeable groups displaying either a bulk like dissociation behavior or forming ionic complexes inside the hydrogel film.

Self-assembly of long chain fatty acids: effect of a methyl branch.

The morphology and molecular conformation of Langmuir-Blodgett deposited and floating monolayers of a selection of straight chain (eicosanoic acid, EA), iso (19-methyl eicosanoic acid, 19-MEA), and anteiso (18-methyl eicosanoic acid, 18-MEA) fatty acids have been investigated by Vibrational Sum Frequency Spectroscopy (VSFS), AFM imaging, and the Langmuir trough. While the straight chain fatty acid forms smooth, featureless monolayers, all the branched chain fatty acids display 10-50 nm sized domains (larger for 19-MEA than the 18-MEA) with a homogeneous size distribution. A model is suggested to explain the domain formation and size in terms of the branched fatty acid packing properties and the formation of hemispherical caps at the liquid-air interface. No difference between the chiral (S) form and the racemic mixture of the 18-MEA is observed with any of the utilized techniques. The aliphatic chains of the straight chain fatty acids appear to be oriented perpendicular to the sample surface, based on an orientational analysis of VSFS data and the odd/even effect. In addition, the selection of the subphase (neat water or CdCl2 containing water buffered to pH 6.0) used for the LB-deposition has a profound influence on the monolayer morphology, packing density, compressibility, and conformational order. Finally, the orientation of the 19-MEA dimethyl moiety is estimated, and a strategy for performing an orientational analysis to determine the complete molecular orientation of the aliphatic chains of 19-MEA and 18-MEA is outlined and discussed.

Reducing Ice Adhesion to Polyelectrolyte Surfaces by Counterion-Mediated Nonfrozen Hydration Water.

Hydrophilic anti-icing coatings can be energy-effective passive solutions for combating ice accretion and reducing ice adhesion. However, their underlying mechanisms of action remain inferential and are ill-defined from a molecular perspective. Here, we systematically investigate the influence of the counterion identity on the shear ice adhesion strength to cationic polymer coatings having quaternary alkyl ammonium moieties as chargeable groups. Temperature-dependent molecular information on the hydrated polymer films is obtained using total internal reflection (TIR) Raman spectroscopy, complemented with differential scanning calorimetry (DSC) and ellipsometry. Ice adhesion measurements show a pronounced counterion-specific behavior with a sharp increase in adhesion at temperatures that depend on the anion identity, following the order Cl- < F- < SCN- < Br- < I-. Linked to the freezing of hydration water, the specific ordering results from differences in ion pairing and the amount of water present within the polymer film. Moreover, similar effects can be promoted by varying the cross-linking density in the coating while keeping the anion identity fixed. These findings shed new light on low ice adhesion mechanisms and may inspire novel approaches for improved anti-icing coatings.

La3+ and Y3+ interactions with the carboxylic acid moiety at the liquid/vapor interface: Identification of binding complexes, charge reversal, and detection limits.

Specific interactions of yttrium and lanthanum ions with a fatty acid Langmuir monolayer were investigated using vibrational sum frequency spectroscopy. The trivalent ions were shown to interact with the charged form of the carboxylic acid group from nanomolar concentrations (<300 nM). Analysis of the spectral features from both the symmetric and the asymmetric carboxylate modes reveals the presence of at least three distinct coordination structures linked to specific binding configurations. Although the same species were identified for both La3+ and Y3+, they display a different concentration dependence, highlighting the ion-specificity of the interaction. From the analysis of the response of interfacial water molecules, the reversal of the surface charge, as well as the formation of yttrium hydroxide complexes, were detected upon increasing the amount of salt in solution. The binding interaction and kinetics of absorption are sensitive to the solution pH, showing a distinct ion speciation in the interfacial region when compared to the bulk. Changing the subphase pH or adding a monovalent background electrolyte that promotes deprotonation of the carboxylic acid headgroup could further improve the detection limit of La3+ and Y3+ to concentrations < 100 nM. These findings demonstrate that nM concentrations of trace metals contaminants, typically found on monovalent salts, can significantly influence the binding structure and kinetics in Langmuir monolayers.

Preferential adsorption of amino-terminated silane in a binary mixed self-assembled monolayer.

The composition and structure of a binary mixed self-assembled monolayer (SAM) of 3-aminopropyltriethoxysilane (APS, NH(2)(CH(2))(3)Si(OCH(2)CH(3))(3)) and octadecyltrimethoxysilane (ODS, CH(3)(CH(2))(17)Si(OCH(3))(3)) on a silicon oxide surface have been characterized by water contact-angle measurements, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and sum frequency generation (SFG) vibrational spectroscopy. XPS demonstrated that APS in the mixed SAM is significantly enriched in comparison to that in solution, indicating the preferential adsorption of APS during the SAM formation. AFM observations showed that the mixed SAM becomes rougher. SFG revealed that the coadsorption of APS induced a conformation disordering in the ODS molecules present in the mixed SAM. The surface enrichment of APS has been explained in terms of differences in the surface adsorption rates of the two components as well as in the self-congregation states of APS molecules in the bulk solution. Furthermore, the structure of the water molecules on the mixed SAM surface in contact with the aqueous solutions at different pH's has also been studied. The results indicate that the mixed-SAM modified surface is positively charged at pH < 5 and negatively charged at pH > 7.

Anion Specific Effects at Negatively Charged Interfaces: Influence of Cl-, Br-, I-, and SCN- on the Interactions of Na+ with the Carboxylic Acid Moiety.

Unlike counterion interactions with charged interfaces, the influence of co-ions is only scarcely reported in the literature. In this work, the effect of SCN- and the halide co-ions in the interactions of Na+ with carboxylic acid Langmuir monolayers is investigated by using vibrational sum frequency spectroscopy. At 1 M concentrations in the subphase, the identity of the anion is shown to have a remarkable influence on the charging behavior and degree of deprotonation of the monolayer, with ions ordering in the sequence I- > SCN- > Cl- ≈ Br-. The same trend is observed at both pH 6 and pH 9 when the monolayer is intrinsically more charged. Spectroscopic evidence is found for both the presence of I- and SCN- in the interfacial region at levels close to their detection limits. The results contradict electrostatic theories on charged interfaces where co-ions are not expected to play any significant role. The higher propensity for the large polarizable anions to deprotonate the monolayer is explained in terms of their ability to modify the cations affinity toward the carboxylic acid groups present at the surface.

Phospholipid monolayers probed by vibrational sum frequency spectroscopy: instability of unsaturated phospholipids.

The surface specific technique vibrational sum frequency spectroscopy has been applied to in situ studies of the degradation of Langmuir monolayers of 1,2-diacyl-phosphocholines with various degrees of unsaturation in the aliphatic chains. To monitor the degradation of the phospholipids, the time-dependent change of the monolayer area at constant surface pressure and the sum frequency intensity of the vinyl CH stretch at the carbon-carbon double bonds were measured. The data show a rapid degradation of monolayers of phospholipids carrying unsaturated aliphatic chains compared to the stable lipids carrying fully saturated chains when exposed to the ambient laboratory air. In addition, the degradation of the phospholipids can be inhibited by purging the ambient air with nitrogen. This instability may be attributed to spontaneous degradation by oxidation mediated by various reactive species in the air. To further elucidate the process of lipid oxidation in biological membranes artificial Langmuir monolayers probed by a surface specific spectroscopic technique as in this study can serve as a model system for studying the degradation/oxidation of cell membrane constituents.

Molecular structure upon compression and stability toward oxidation of Langmuir films of unsaturated fatty acids: a vibrational sum frequency spectroscopy study.

Vibrational sum frequency spectroscopy (VSFS) has been used to determine the stability toward oxidation in air of a series of unsaturated fatty acids, measuring as a function of time the changes in the chemical structure and conformational order of films spread on a Langmuir trough. The fatty acids studied consisted of a 20-carbon backbone with increasing numbers of cis double bonds in the chain: 11c-eicosenoic acid (20:1 EA, omega-9), 11c,14c-eicosadienoic acid (20:2 EA, omega-6), and 11c,14c,17c-eicosatrienoic acid (20:3 EA, omega-3). Measurements at constant surface pressure show that double bonds are lost from the surface region and that drops in intensity of the vinyl CH stretch are detectable within a few minutes of spreading the monolayer. The results are consistent with the fatty acid peroxidation free radical mechanism. The sum frequency spectra also reveal that what remains on the surface is conformationally more disordered with a larger number of gauche defects. The oxidation kinetics are found to be strongly dependent on the packing density of the monolayer, being more stable at higher pressures. Oxidation can be avoided by purging the system in an inert atmosphere. Finally, the molecular structure upon compression was tracked in unoxidized monolayers. The results suggest that the packing and orientation of the double bond sections of all three unsaturated fatty acids show remarkable similarities, with the direction of the double bonds approximately parallel to each other irrespective of the number of unsaturations in the chain, with the 20:3 EA probably forming "iron-angle" structures. The possibility of unsaturated chains in a "hairpin" configuration is discarded for area per molecules smaller than approximately 50 A(2), which corresponds to the lowest surface pressure measured with VSFS.

Identifying Eigen-like hydrated protons at negatively charged interfaces.

Despite the importance of the hydrogen ion in a wide range of biological, chemical, and physical processes, its molecular structure in solution remains lively debated. Progress has been primarily hampered by the extreme diffuse nature of the vibrational signatures of hydrated protons in bulk solution. Using the inherently surface-specific vibrational sum frequency spectroscopy technique, we show that at selected negatively charged interfaces, a resolved spectral feature directly linked to the H3O+ core in an Eigen-like species can be readily identified in a biologically compatible pH range. Centered at ~2540 cm-1, the band is seen to shift to ~1875 cm-1 when forming D3O+ upon isotopic substitution. The results offer the possibility of tracking and understanding from a molecular perspective the behavior of hydrated protons at charged interfaces.

Adsorption of CTAB on hydrophilic silica studied by linear and nonlinear optical spectroscopy.

Vibrational sum-frequency spectroscopy (SFS) and total internal reflection Raman scattering (TIR Raman) have been used to study the adsorption of hexadecyltrimethylammonium bromide (CTAB) to hydrophilic silica. These two complementary techniques permit the determination of the adsorbed amount with a sensitivity of approximately 1% of the maximum surface coverage, changes in the average tilt of the adsorbed molecules, the presence of asymmetric aggregates in the adsorbed film, and the structure and orientation of the water molecules in the interfacial region. The TIR Raman spectra show a monotonic increase with CTAB concentration with no measurable changes in the relative intensities of the different polarization combinations probed, implying that no significant changes occur in the conformational order of the hydrocarbon chain. In the sum-frequency (SF) spectra, no detectable peaks from the surfactant headgroup and hydrophobic chain were observed at any surface coverage. Major changes are observed in the water bands of the SF spectra, as the originally negatively charged silica surface becomes positively charged with an increase in the adsorbed amount, inducing a change in the polar orientation of the water molecules near the surface. The detection limits for hydrocarbons chains in the SF spectra were estimated by comparison with the SF spectrum of a disordered octadecyltrichlorosilane monolayer. The simulations demonstrate that the asymmetry in the adsorbed CTAB layer at any concentration is less than 5% of a monolayer. The results obtained pose severe constraints on the possible structural models, in particular at concentrations below the critical micellar concentration where information is scarce. The formation of hemimicelles, monolayers and other asymmetric aggregates is ruled out, with centrosymmetric aggregates forming from early on in the adsorption process.