Ions at the air/water interface

In a recent review of this topic [B.C. Garett, Science 303 (2004) 1146] the emphasis was on some recent experiments, in which it was found that some anions accumulate at the air/water interface and not in the bulk, as usually happens to the cations, and on some simulations which explained those positive surface adsorption excesses. Because a large number of these experiments could be explained on the basis of some simple physical models proposed by the authors for the interaction between the ions and the air/water interface [M. Manciu, E. Ruckenstein, Adv. Colloid Interface Sci. 105 (2003) 63; Adv. Colloid Interface Sci. 112 (2004) 109; Langmuir 21 (2005) 11312], those models are reviewed in the present note, the goal being to draw attention to them.     

Electronic states at the water/air interface

Using combined path integral-molecular dynamics simulation techniques, we analyze electronic solvation at the water/air interface. Superficial electrons present a considerable extent of spatial confinement, somewhat less marked but still comparable to that found in bulk. The characteristics of the interfacial polarization promote an overall structure for the solvated electron-polymer which looks flatter along the direction perpendicular to the interface. Spatial and orientational responses of different slabs in the close vicinity of the interface were also investigated. Solvent configurations obtained from the simulations have been used to analyze electronic excited states and the optical absorption spectrum of superficial electrons. Compared to bulk results, the distribution of bound electronic states at the surface presents similar characteristics, that is, a ground s-state and three, quasi-degenerate, p-like excited states. The reduction of the energy gap between the ground state and the rest of excited states leads to a approximately 0.52 eV red-shift in the position of the absorption maximum.     

Protein-lipid interactions at the air/water interface

Surface pressure measurements and external reflection FTIR spectroscopy have been used to probe protein-lipid interactions at the air/water interface. Spread monomolecular layers of stearic acid and phosphocholine were prepared and held at different compressed phase states prior to the introduction of protein to the buffered subphase. Contrasting interfacial behaviour of the proteins, albumin and lysozyme, was observed and revealed the role of both electrostatic and hydrophobic interactions in protein adsorption. The rate of adsorption of lysozyme to the air/water interface increased dramatically in the presence of stearic acid, due to strong electrostatic interactions between the negatively charged stearic acid head group and lysozyme, whose net charge at pH 7 is positive. Introduction of albumin to the subphase resulted in solubilisation of the stearic acid via the formation of an albumin-stearic acid complex and subsequent adsorption of albumin. This observation held for both human and bovine serum albumin. Protein adsorption to a PC layer held at low surface pressure revealed adsorption rates similar to adsorption to the bare air/water interface and suggested very little interaction between the protein and the lipid. For PC layers in their compressed phase state some adsorption of protein occurred after long adsorption times. Structural changes of both lysozyme and albumin were observed during adsorption, but these were dramatically reduced in the presence of a lipid layer compared to that of adsorption to the pure air/water interface.     

Polymer/surfactant interactions at the air/water interface

The development of neutron reflectometry has transformed the study and understanding of polymer/surfactant mixtures at the air/water interface. A critical assessment of the results from this technique is made by comparing them with the information available from other techniques used to investigate adsorption at this interface. In the last few years, detailed information about the structure and composition of adsorbed layers has been obtained for a wide range of polymer/surfactant mixtures, including neutral polymers and synthetic and naturally occurring polyelectrolytes, with single surfactants or mixtures of surfactants. The use of neutron reflectometry together with surface tensiometry, has allowed the surface behaviour of these mixtures to be related directly to the bulk phase behaviour. We review the broad range of systems that have been studied, from neutral polymers with ionic surfactants to oppositely charged polyelectrolyte/ionic surfactant mixtures. A particular emphasis is placed upon the rich pattern of adsorption behaviour that is seen in oppositely charged polyelectrolyte/surfactant mixtures, much of which had not been reported previously. The strong surface interactions resulting from the electrostatic attractions in these systems have a very pronounced effect on both the surface tension behaviour and on adsorbed layers consisting of polymer/surfactant complexes, often giving rise to significant surface ordering.     

Cyclodextrin-based self-assembled nanotubes at the water/air interface

Native alpha-cyclodextrin (alpha-CD) is found to spontaneously form films at aqueous solution/air interfaces. Shape-response measurements to volume perturbations on drops hanging from a capillary indicate that temperature and sodium dodecyl sulfate (SDS) concentration strongly modify the viscoelastic properties of such films. By using isothermal titration calorimetry (ITC), Brewster angle microscopy (BAM), atomic force microscopy (AFM), and molecular dynamics (MD) simulations, it is shown that the films consist of self-assembled nanotubes whose building blocks are cyclodextrin dimers (alpha-CD2) and alpha-CD2-SDS1 complexes.     

Surfactant headgroup orientation at the air/water interface

We have used vibrational sum-frequency spectroscopy to provide the first measurement of the spectrum and orientation of the polar headgroup of a charged alkyl surfactant at the air/water interface. Sum-frequency spectra of sodium dodecyl sulfate (SDS) are used to arrive at all participating elements of the second-order susceptibility tensor. We use these chi(2) elements, together with calculated values of the hyperpolarizability, to determine the tilt of the S-O bond attached to the alkyl chain and the twist of the S-O-C plane. Thus, a full characterization of the orientation of the surfactant headgroup has been achieved. This is the first demonstration of the feasibility of sum-frequency measurements of sulfate modes in the 1100 cm-1 region, opening possibilities for future investigations of surfactant behavior in this spectral region at aqueous and solid interfaces.     

Cationic Gemini surfactant at the air/water interface

The surface properties and structures of a cationic Gemini surfactant with a rigid spacer, p-xylyl-bis(dimethyloctadecylammonium bromide) ([C(18)H(37)(CH(3))(2)N(+)CH(2)C(6)H(4)CH(2)N(+)(CH(3))(2)C(18)H(37)],2Br(-), abbreviated as 18-Ar-18,2Br(-1)), at the air/water interface were investigated. It is found that the surface pressure-molecular area isotherms observed at different temperatures do not exhibit a plateau region but display an unusual "kink" before collapse. The range of the corresponding minimum compressibility and maximum compressibility modulus indicates that the monolayer is in the liquid-expanded state. The monolayers were transferred onto mica and quartz plates by the Langmuir-Blodgett (LB) technique. The structures of monolayers at various surface pressures were studied by atomic force microscopy (AFM) and UV-vis spectroscopy, respectively. AFM measurements show that at lower surface pressures, unlike the structures of complex or hybrid films formed by Gemini amphiphiles with DNA, dye, or inorganic materials or the Langmuir film formed by the nonionic Gemini surfactant, in this case network-like labyrinthine interconnected ridges are formed. The formation of the structures can be interpreted in terms of the spinodal decomposition mechanism. With the increase of the surface pressure up to 35 mN/m, surface micelles dispersed in the network-like ridges gradually appear which might be caused by both the spinodal decomposition and dewetting. The UV-vis adsorption shows that over the whole range of surface pressures, the molecules form a J-aggregate in LB films, which implies that the spacers construct a pi-pi aromatic stacking. This pi-pi interaction between spacers and the van der Waals interaction between hydrophobic chains lead to the formation of both networks and micelles. The labyrinthine interconnected ridges are formed first because of the rapid evaporation of solvent during the spreading processes; with increasing surface pressure, some of the alkyl chains reorient from tilting to vertical, forming surface micelles dispersed in the network-like ridges due to the strong interaction among film molecules.     

Adsorption of polyprotic acid at the water/air interface

A rigorous thermodynamic treatment appropriate for surface adsorption from mixed aqueous solution of alkali and polyprotic acid was derived. Those equations were applied to mixed aqueous solution/air systems of alkali metal hydroxide and Fe^III complex with ethylenediamine- N, N, N′,N′-tetraacetate (Fe-EDTA). Surface density of each species arising from Fe-EDTA was separately evaluated, and thus, surface activity of Fe-EDTA was studied, especially its dependence on pH and how it is influenced by the counter cations. Fe-EDTA was positively adsorbed at the water/air interface at very low pHs and negatively at high pHs. The pH range of positive adsorption of Fe-EDTA with potassium ion, as a counter ion, was wider than that with sodium ion. Thus, potassium ion, a structure breaker, tended to smooth surface adsorption of Fe-EDTA at the water/air interface, whereas sodium ion, a structure maker, tended to withdraw Fe-EDTA from the interfacial region.     

Ozonolysis of uric acid at the air/water interface

Uric acid (UA) epoxide, peroxide, and ozonide species produced in aqueous UA microdroplets exposed to O(3)(g) are detected by online mass spectrometry within approximately 1 ms. UA conversions are independent of its initial concentration below approximately 0.1 mM and are unaffected by addition of excess H(2)O(2) or t-butanol. UA reactivity increases approximately 380 times from pH 4 to 7, which is at variance with the pH-independent rates reported for the UA + O(3)(aq) reaction in bulk water. At pH approximately 7, UA and ascorbic acid (AH(2)) microdroplets react with O(3)(g) at similar rates, although UA is approximately 40 times more reactive than AH(2) toward O(3)(aq) in bulk water. Only the UA epoxide, plus traces of UA peroxide, are formed upon mixing UA(aq) and O(3)(aq) solutions. We infer that the gas-liquid ozonolysis of UA proceeds in an interfacial aqueous medium quite distinct from bulk water. Thus, UA, a component of the pulmonary epithelial lining fluid that scavenges atmospheric O(3)(g) into less deleterious species (similar to AH(2)), is rendered inactive below pH approximately 5. The potential implications of these findings on synergistic health effects between tropospheric ozone and acidic particulates are briefly analyzed.     

Nystatin in Langmuir monolayers at the air/water interface

The paper presents a thorough characteristics of Langmuir monolayers formed at the air/water interface by a polyene macrolide antibiotic-nystatin. The investigations are based on the analysis of pi/A isotherms recorded for monolayers formed by this antibiotic at different experimental conditions. A significant part of this work is devoted to the stability and relaxation phenomena. It has been found that nystatin forms at the air/water interface monolayers of the LE state. A plateau region, observed during the course of the isotherm compression, is suggested to be due to the orientational change of nystatin molecules from horizontal to vertical position. Quantitative analysis of the desorption of the monolayer material into bulk water indicates that the solubility of nystatin monolayers increases with surface pressure. At low surface pressures, the desorption of nystatin from a monolayer is controlled both by dissolution and by diffusion. However, at the plateau and in the post-plateau region, the desorption does not achieve a steady state and the monolayer is less stable than in the pre-plateau region. However, the presence of membrane lipids, even at a low mole fraction, considerably increases the stability of nystatin monolayers. This enables the application of the Langmuir monolayer technique to study nystatin in mixture with cellular membrane components, aiming at verifying its mode of action and the mechanism of toxicity.     

Insoluble monolayers of irisresorcinol at the air/water interface

Monolayer properties of irisresorcinol [5-(cis-10-heptadecenyl) resorcinol] were measured at the air/water interface. TheA-T isobars of the monolayers at 10 and 15 mN/m gave two-dimensional thermal expansivities of 1.4 × 10^–4/K and 1.3 × 10^–4/K at a temperature span from 7–40 C, respectively. The- A isotherms of the material showed only a little dependence on temperature from 5–35 C and onpH except at highpH, where monolayers expanded by ionization of resorcinol headgroups. Some types of saccharose in the subphase exhibited a characteristic interaction with irisresorcinol in monolayers, and there is a possibility that this material will be used for molecular recognition of some saccharoses.     

Polydiacetylene-supported silica films formed at the air/water interface

Mesostructured silica films have attracted interest as potential platforms for sensing, molecular sieving, catalysis, and others. The fabrication of free-standing silica films on water, however, is challenging due to the need for scaffolding agents that would constitute effective templates. We describe the assembly of thin film at the air/water interface comprising quaternary silicates and polydiacetylene (PDA), a unique chromatic polymer forming two-dimensional conjugated networks, and the use of these films for biological sensing. PDA exhibits a dual role in the system-both as the amphiphilic matrix facilitating immobilization of the silicate colloidal units at the air/water interface and additionally a chromatic reporter that undergoes visible blue-red transitions, accompanied by fluorescence transformations, in the presence of analytes. We demonstrate the application of the silicate/PDA thin films for the detection of bacterial proliferation.     

Adsorption of sugar surfactants at the air/water interface

The adsorption isotherms of n-decyl-β-D-glucoside (β-C(10)G(1)) as well as various n-alkyl-β-D-maltosides (β-C(n)G(2)) with n=8, 10, 12 and 14 were determined from surface tension measurements. Based on the analysis of the adsorption isotherms, the total free energy change of adsorption was determined and a novel method was proposed to determine the maximum adsorbed amount of surfactant. It can be concluded that the driving force for adsorption first increases with increasing adsorbed amount of the sugar surfactants and then levels off in a plateau. This peculiar behaviour is interpreted as formation of a thin liquid-like alkane film of overlapping alkyl chains at the air/water interface once a certain adsorbed amount is exceeded. The driving force of adsorption depends on the alkyl chain length only and is not affected by the type of the head group. The hydrophobic contribution to the standard free energy change of adsorption was compared with the values of sodium alkylsulfate and alkyltrimethylammonium bromide surfactants. This comparison reveals that the hydrophobic driving force of adsorption is the largest for the sodium alkylsulfates, whereas it is the same for the sugar surfactants and the alkyltrimethylammonium bromides.     

Adsorption behavior of oxyethylated surfactants at the air/water interface

The low-shear viscosity eta(0) of colloidal suspensions of acrylic latex or silica in aqueous gelatin has been measured at a temperature above the sol-gel transition. Measurements were made on dilution of a concentrated suspension with water or a gelatin solution. Thus, either the gelatin : colloid ratio was maintained or it was varied at constant aqueous gelatin concentration. Systems were studied with four lime-processed gelatins of different molecular weights at two concentrations of added salt. In addition, the latex particle size and the thickness of the adsorbed gelatin layer were measured by photon correlation spectroscopy (PCS) under dilute conditions. The dependence of the low-shear viscosity eta(0) on particle concentration was exponential and did not follow the well-established Krieger-Dougherty model for simple hard-sphere suspensions over the concentration range studied. A simple phenomenological model, eta(0)=eta(o)10(phi(e)/phi(s)), was found to predict the behavior well. Here, eta(o) is the viscosity of a gelatin solution of the corresponding solution concentration, phi(e) is proportional to the volume fraction of the particles, and phi(s) is a scaling factor, which was determined to have a value of 0.85. With this value of phi(s), the dimensions determined from PCS could be used to predict the viscosity values.     

Gold and silver nanorings formed at the air/water interface

Gold nanorings were prepared at the air/water interface through reduction of AuCl₄⁻ ions by UV-light irradiation or formaldehyde gas treatment at room temperature templated by thin films of phthalocyanine derivatives. Silver nanorings were produced at the air/water interface via reduction of Ag⁺ ions by UV-light irradiation templated by poly(9-vinylcarbazole) (PVK) thin films. These nanostructures were investigated by transmission electron microscopy (TEM), selective-area electron diffractometry (SAED), and high-resolution TEM (HRTEM). It was found that the gold nanorings are composed of close-packed nanoplates whose (1 1 0) crystal planes are parallel to the air/water interface; while silver rings are composed of nanoparticles. It is demonstrated that the ring-like aggregates formed by parallel linear supramolecules of the phthalocyanine derivatives and the ring-like structure of PVK supramolecules are responsible for the formation of the gold and silver nanorings, respectively.     

Viscoelastic properties of insoluble amphiphiles at the air/water interface

The effects of the presence of a molecular monolayer on the dilatational properties of the air/water interface have been investigated. Two water insoluble amphiphiles, dipalmitoyl phosphatidyl choline and quercetin 3-O-palmitate, were spread onto a pendant drop and the dynamic surface pressure was measured by means of drop shape analysis. The surface dilatational elasticity and viscosity of the spread monolayers were also determined by the oscillating drop technique. Constraints on the range of measuring conditions were investigated and we demonstrated that the pressure-area isotherms derived from oscillatory dynamic measurements display phase behaviour similar to that found in equilibrium measurements, albeit at reduced resolution. Both the amphiphiles formed purely elastic films that were characterised by a dilatational modulus that depended on the surface concentration and obeyed a power scaling law. The exponent of the relationship could be related to the thermodynamic conditions prevailing at the interface. The phospholipid monolayer scaling exponent was 2.8 in a temperature range of 20-26 degrees C indicates a favourable solvency of molecules in the bidimensional matrix. A very high scaling exponent (11.8 at 7 degrees C) for quercetin palmitate was interpreted assuming that molecules self-organise in fibre-like structures. This interface structure and the phase behaviour was found consistent with observations of the surface film obtained by Brewster angle microscopy. The structured quercetin 3-O-palmitate monolayers are disrupted by temperature increase or by adding a 0.2 molar fraction of the immiscible dipalmitoyl phosphatidyl choline.     

Adsorption of alkyl trimethylammonium bromides at the air/water interface

A number of features of the adsorption of alkyl trimethylammonium bromides with nc=10,12,14, and 16 at the air/water interface were studied. First, the adsorption isotherms were calculated from experimental surface tension vs concentration curves by means of the Gibbs equation. Second, a novel method was used to estimate the adsorption free energy change. From the analysis of these data it was concluded that the hydrophobic driving force for the adsorption first increases with increasing adsorbed amount and then levels off in a plateau, which holds true for all four homologues. This peculiar behavior was interpreted by the formation of a thin liquid-like alkane film at the air/water interface once a certain adsorbed amount is exceeded. The hydrophobic contribution to the standard free energy change of adsorption was compared with those values previously determined for alkyl sulfate homologues. This comparison suggests that the alkyl trimethylammonium type surfactants behave as if their alkyl chain was approximately one methylene group shorter than those of the corresponding alkyl sulfates.     

Interaction of nitrophenols with lipids at the air/water interface

The uptake of ortho and para nitrophenol to charged and neutral lipid monolayers spread at the air/solution interface was studied by reflection spectroscopy. The adsorption characteristics of the two nitrophenols have been studied by measuring the surface pressure and surface potential as a function of molecular area of the different lipid monolayers in the presence of nitrophenols in the subphase. The results have been interpreted in terms of the electrostatic interaction between the negatively charged dissociated phenolate ions and the positively charged head group of dioctadecyldimethylammonium bromide monolayers.     

Characterization of peptide-guided polymer assembly at the air/water interface

An organo-soluble, peptide-polymer conjugate that combines poly(n-butyl acrylate) with a beta-sheet-forming peptide is spread at the water surface to investigate peptide-guided self-assembly in a two-dimensional environment. Single layers of the conjugate are studied to gain information on the packing, orientation, and structure of the conjugate molecules using standard monolayer techniques: isotherms, grazing incidence X-ray diffraction (GIXD), and infrared reflection absorption spectroscopy (IRRAS). At all conditions studied, the stabilizing beta-sheet network consists of antiparallel beta-sheets oriented parallel to the air/water interface. The incorporation of temporary switch defects in the peptide segment enables beta-sheet assembly to be triggered at different packing densities. Stable monolayers, with low compressibilities similar to peptide monolayers, form when beta-sheet assembly occurs in monolayers that contain closely packed conjugate molecules. Langmuir-Schaefer transfer of the switched monolayer seeded with 1/1000 part stearic acid results in a transferred monolayer containing ordered domains with 7 nm wide stripes, a width in agreement with the end-to-end distance of the conjugate molecule. In this interfacial system, high packing densities and a hydrophobic seed molecule play an important role in beta-sheet network and structure formation. Both effects likely direct the highly ordered beta-sheet structure because of beta-strand prealignment. Insights gained from self-assembly in this system can be applied to peptide aggregation mechanisms in more complex interfacial environments.