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.     

Studies on the electrical double layer structure at the water/air interface

Effective dipole moments (calculated from experimental data of surface tension and electric surface potential) of some homologous normal alcohols and carboxylic acid were found to vary linearly with the number of carbon atoms in the hydrocarbon chain. Values of effective dipole moments were used for the determination of the effective dipole moments of water molecules , and the dielectric permittivity of the water subphase (₁), as well as in the vicinity of the hydrophobic part of adsorbed molecule (₂). The latter was found to decrease with the increase of the hydrocarbon chain length. Knowing the effective dipole moment of surface water dipoles, the average orientation angle () of water molecules at the inteface was estimated. The calculated potential drop of water varies within the range –0.038 to –2.38 V for two extreme orientations of water dipoles at the surface.     

Synthesis of ultra-thin films of aromatic polymers at air/water interface

Ultra-thin films of and precursor polymers for polybenzimidazole (PBI), polybenzoxazole (PBO), or polybenzothiazole (PBT) were formed at air/water interface by spreading monomers and then polymerizing on the water surface. These thin films could be deposited onto appropriate substrates by using the LB method of horizontal lifting. Moreover, the heat-treatment of the built-up films of the precursor polymers of PBI, PBO, and PBT formed the ultra-thin films of high temperature polymers. The resulting ultra-thin films had uniform and controllable thickness, but remained fairly stable when subjected to temperature up to 300°C. They also had good solvent resistance.     

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.     

Electron hopping dynamics in Au38 nanoparticle langmuir monolayers at the air/water interface

The electron-transfer dynamics between nanoparticles has been studied as a function of interparticle distance by in situ voltammetry of well-defined monolayers of a metal quantum dot nanoparticle Au38(hexanethiolate)24. The interparticle distance is precisely controlled by the Langmuir technique and addition of various lengths of dithiol linkers (HS(CH2)nSH; n = 5, 6, 8, and 9). Voltammograms of Au38 monolayers display a well-defined single-electron charging peak that increases remarkably with decreasing the interparticle distance. The diffusion coefficient and rate constant calculated from the peak current for core-core electron hopping reaction both exponentially increase respectively, from 3.3 x 10-10 to 5.2 x 10-9 cm2/s and 2.2 x 104 to 5.0 x 105 s-1 as the distance decreases from 13.3 to 9.5 A and then levels off at 8.0 A. These rate constants are in good agreement with the literature values, demonstrating that the present experimental approach provides a powerful way to investigate the correlation between the electron-transfer dynamics and nanoparticle assembly structure.     

Nanoaggregate shapes at the air/water interface

Chiral interfaces and molecular recognition phenomena are of special interest not only for the understanding of biological recognition processes but also for the potential application in material science. Langmuir monolayers at the air-water interface have successfully been used as simple models to mimic biological phenomena. Recent experimental studies revealed that both chirality and molecular recognition processes of amphiphiles are controlling the features of the nano-aggregates at the air/water interface. The objective of experimental studies has been to gain information about the properties of mesoscopic length scale aggregates obtained on the basis of chiral discrimation effects and the formation of supramolecular entities by molecular recognition of non-surface active species dissolved in the aqueous subphase. Differences in the two-dimensional morphology and lattice structures of the nano-aggregates cannot be explained by macroscopic theories and needed information about the detailed orientation and distance dependence of the intermolecular interaction within the aggregates. First new bottom-up studies have been directed toward understanding the driving forces for the aggregation processes of monolayers. Different types of interactions have been successfully considered using semi-empirical quantum chemical methods. The possibilities of Langmuir-Blodgett (LB) patterning to be an alternative paradigm for large-area patterning with mesostructured features are discussed.     

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.     

The structure of adsorbed films of some aliphatic compounds at the water/air interface

Electric surface potential (V) and surface tension measurements of aqueous solutions of some aliphatic compounds were used to determine the surface activity, orientation of molecules at the water/air interface, effective dipole moments (connected with water molecules, hydrophilic and hydrophobic groups), and local dielectric permittivities of the surface layer.     

Polystyrene-block-poly(ethylene oxide) stars as surface films at the air/water interface

Star diblock copolymers containing polystyrene (PS) and poly(ethylene oxide) (PEO) were investigated as surface films at the air/water interface. Both classic and dendritic-like stars were prepared containing either a PS core and PEO corona or the reverse. The investigated polymers, consisting of systematic variations in architectures and compositions, were spread at the air/water interface, generating reproducible surface pressure-area isotherms. All of the films could be compressed to higher pressures than would be possible for pure PEO. For stars containing 20% or more PEO, three distinct regions appeared. At higher areas, the PEO absorbs in pancakelike structures at the interface with PS globules sitting atop. Upon compression, a pseudoplateau transition region appeared. Both regions strongly depended on PEO composition. The pancake area and the pseudoplateau width and pressure increased in a linear fashion with an increasing amount of PEO. In addition, minimum limits of PEO chain length and mass percentage were determined for observing a pseudoplateau. At small areas, the film proved less compressible, producing a rigid film in which PS dominated. Here, the film area increased with both molecular weight and the amount of PS. Comparison with pure linear PS showed the stars spread more, occupying greater areas. Among the stars, the PEO-core stars were more compact while the PS-core stars spread more. The influence of architecture in terms of the core/corona polymers and branching were also examined. The effects of architecture were subtle, proving less important than PEO chain length or mass percentage.     

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.     

Charge reversal at the air/water interface as inferred from the thickness of foam films

Experiments are reported with foam films from aqueous solutions with increasing concentration of a cationic surfactant. A correlation is established between the foam film thickness and the possible variation of diffuse electric layer potential at the air/water interface from a negative value in absence of surfactant to positive values at higher surfactant concentrations. It is concluded that a charge reversal at the air/water interface is expected to occur under increasing concentration of cationic surfactants in aqueous solutions.     

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.     

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.     

Aggregation states and molecular motion of polymer ultrathin films prepared at the air/water interface

Surface structure and dynamics in three different polymeric ultrathin systems, such as organosilane monolayers, poly(methyl methacrylate) (PMMA) brushes and poly(amido amine) dendrimer monolayers are discussed.     

Macroporous honeycomb films of surfactant-encapsulated polyoxometalates at air/water interface and their electrochemical properties

A series of surfactant-encapsulated polyoxometalates which have different compositions, shapes, and sizes, are able to self-assemble to the highly ordered honeycomb-structured macroporous films at the air/water interface without any extra moist airflow across the solution surface. The honeycomb film pores in the average diameter of 2-3 μm are obtained, which are independent of the polyoxometalates. It is speculated that the cooled micrometer water droplets act as the necessary templates for the formation of macropores, and the stability of these water droplets is crucial during the self-assembly. With increasing the concentration of surfactants, various morphologies from lowly ordered honeycomb films to highly ordered honeycomb films and then to disordered fragments can be modulated. The interfacial tension between chloroform solution and water droplets induces the changes of films. High-resolution TEM observations indicate a close-packed lamellar structure in the ordered honeycomb film walls. The self-assembly successfully performs the transfer of functional polyoxometalates from bulk solutions to interfacial films. Consequently, the produced honeycomb films present electronic activities, such as ferromagnetism and electrochemical properties. These detailed researches will enrich the studies based on materials obtained by encapsulations in cationic surfactants to construct newly nanostructures of polyoxometalates at interfaces, and promote the potential applications of the honeycomb films of surfactant-encapsulated polyoxometalates in advanced materials.     

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.