Advances in Colloid and Interface Science (v.154, #1-2)

Recent work has provided experimental and theoretical evidence that a first order fluid/condensed (LE/LC) phase transition can occur in adsorbed monolayers of amphiphiles and surfactants which are dissolved in aqueous solution. Similar to Langmuir monolayers, also in the case of adsorbed monolayers, the existence of a G/LE phase transition, as assumed by several authors, is a matter of question. Representative studies, at first performed with a tailored amphiphile and later with numerous other amphiphiles, also with n-dodecanol, provide insight into the main characteristics of the adsorbed monolayer during the adsorption kinetics. The general conditions necessary for the formation of a two-phase coexistence in adsorbed monolayers can be optimally studied using dynamic surface pressure measurements, Brewster angle microscopy (BAM) and synchrotron X-ray diffraction at grazing incidence (GIXD). A characteristic break point in the time dependence of the adsorption kinetics curves indicates the phase transition which is largely affected by the concentration of the amphiphile in the aqueous solution and on the temperature. Formation and growth of condensed phase domains after the phase transition point are visualised by BAM. As demonstrated by a tailored amphiphile, various types of morphological textures of the condensed phase can occur in different temperature regions. Lattice structure and tilt angle of the alkyl chains in the condensed phase of the adsorbed monolayer are determined using GIXD. The main growth directions of the condensed phase textures are correlated with the two-dimensional lattice structure. The results, obtained for the characteristics of the condensed phase after a first order main transition, are supported by experimental bridging to the Langmuir monolayers. Phase transition of adsorbing trace impurities in model surfactants can strongly affect the characteristics of the main component. Dodecanol present as minor component in aqueous sodium dodecylsulfate solution dominate largely the fundamental features of the adsorbed monolayer of the mixed dodecanol/SDS solutions at adsorption equilibrium.A theoretical concept on the basis of the quasi-chemical model and assumption of the entropy non-ideality has been developed which can well describe the experimental results of the diffusion kinetics of surfactant adsorption from solutions. The model regards the phase behaviour of adsorbed monolayers on the basis of the experimental results explicitly supported by the first order fluid/condensed phase transition and theoretical models assuming bimodal distribution between large aggregates (domains) and monomers and/or very small aggregates. Another simple theoretical model for the description of the coadsorption of surfactant mixtures, based on the additivity of the contributions brought by the solution components into the surface pressure is shown to be in qualitative agreement with the experimental data of mixed dodecanol/SDS solutions. The theoretical results corroborate the fact that the formed condensed phase (large aggregates) in the mixed monolayer consists mainly of dodecanol.
Keywords: Adsorption; Phase transition; Monolayer; BAM; GIXD;

Two-dimensional nanoarchitectonics based on self-assembly by Katsuhiko Ariga; Michael V. Lee; Taizo Mori; Xiao-Yan Yu; Jonathan P. Hill (20-29).
Top–down nanofabrication techniques, especially photolithography, have advanced nanotechnology to a point where system-process integration with bottom–up self-assembly is now required. Because most lithographic techniques are constrained to two-dimensional planes, investigation of integrated self-assembly systems should focus on two-dimensional organization. In this review, research on two-dimensional nanoartchitectonics is classified and summarized according to the type of interface used. Pattern formation following deposition of vaporized molecules onto a solid surface can be analyzed with high structural precision using scanning probe microscopy under ultra high vacuum. Transitions of adsorbed phases and adjustment of pattern mismatch by conformational changes of adsorbed molecules are discussed, in addition to the forces constraining pattern formation, i.e., two-dimensional hydrogen bond networks, van der Waals forces, and molecule–surface interactions. Molecular deposition at a liquid–solid interface broadens the range of molecules that can be investigated. The more complex molecules discussed in this work are C60-fullerene derivatives and designer DNA strands. Gas–liquid interfaces, e.g. between air and water, allow dynamic formations that can adjust to molecular conformational changes. In this case, any resulting patterns can be modulated by varying conditions macroscopically. Using flexible molecules at the fluid air–water interface also permits dynamic operation of molecular machines by macroscopic mechanical motion, thus enabling, hand-operated nanotechnology.
Keywords: Two-dimensional; Self-assembly; Interface; Pattern; Molecular recognition; Nanotechnology;

Nanobubbles and the nanobubble bridging capillary force by M.A. Hampton; A.V. Nguyen (30-55).
Interactions between hydrophobic surfaces at nanometer separation distances in aqueous solutions are important in a number of biological and industrial processes. Force spectroscopy studies, most notably with the atomic force microscope and surface-force apparatus, have found the existence of a long range hydrophobic attractive force between hydrophobic surfaces in aqueous conditions that cannot be explained by classical colloidal science theories. Numerous mechanisms have been proposed for the hydrophobic force, but in many cases the force is an artifact due to the accumulation of submicroscopic bubbles at the liquid–hydrophobic solid interface, the so called nanobubbles. The coalescence of nanobubbles as hydrophobic surfaces approach forms a gaseous capillary bridge, and thus a capillary force. The existence of nanobubbles has been highly debated over the last 15 years. To date, experimental evidence is sound but a theoretical understanding is still lacking. It is the purpose of this review to bring together the many experimental results on nanobubbles and the resulting capillary force in order to clarify these phenomena. A review of pertinent nanobubble stability and formation theories is also presented.
Keywords: Nanobubbles; Nanobubble bridging capillary force; Dissolved gas; Water; Atomic force microscopy;

Symmetry breaking in confined fluids by Eli Ruckenstein; Gersh O. Berim (56-76).
The recent progress in the theoretical investigation of the symmetry breaking (the existence of a stable state of a system, in which the symmetry is lower than the symmetry of the system itself) for classical and quantum fluids is reviewed. The emphasis is on the conditions which cause symmetry breaking in the density distribution for one component fluids and binary mixtures confined in a closed nanoslit between identical solid walls. The existing studies have revealed that two kinds of symmetry breaking can occur in such systems. First, a one-dimensional symmetry breaking occurs only in the direction normal to the walls as a fluid density profile asymmetric with respect of the middle of the slit and uniform in any direction parallel to the walls. Second, a two-dimensional symmetry breaking occurs in the fluid density distribution which is nonuniform in one of the directions parallel to the walls and asymmetrical in the direction normal to the walls. It manifests through liquid bumps and bridges in the fluid density distribution. For one component fluids, conditions of existence of symmetry breaking are provided in terms of the average fluid density, strength of fluid–solid interactions, distance at which the solid wall generates a hard core repulsion, and temperature. In the case of binary mixtures, the occurrence of symmetry breaking also depends on the composition of the confined mixtures.
Keywords: Symmetry breaking; Density functional theory; Canonical-ensemble; Slit-like pores;

Previously, we presented a review of our kinetic models for the nucleation mechanism of protein folding and for the protein thermal denaturation in a barrierless way. A protein was treated as a random heteropolymer consisting of hydrophobic, hydrophilic, and neutral beads. As a crucial idea of the model, an overall potential around the cluster of native residues wherein a residue performs a chaotic motion was considered as the combination of the average dihedral, effective pairwise, and confining potentials. The overall potential as a function of the distance from the cluster has a double well shape. This allowed one to develop kinetic models for the nucleation mechanism of protein folding (NMPF) and barrierless protein denaturation (BPD) by using the mean first passage time analysis. In the original models, however, hydrogen bonding effects were taken into account only indirectly which affected the accuracy of the models because hydrogen bonding does play a crucial role in the folding, stability, and denaturation of proteins. To improve the NMPF and BPD models and explicitly take into account the hydrogen bonding “water–water” and “water–protein residue”, we have developed a probabilistic hydrogen bond (PHB) model for the effect of hydrogen bond networks of water molecules around two solute particles (immersed in water) on their interaction, and have then combined the PHB model with the NMPF and BPD models. In this paper, that can be regarded as sequel of our previous review, we analyze the modified NMPF and BPD models that explicitly take into account the effect of water–water hydrogen bonding on these processes. As expected, the application of the modified models to the folding/unfolding of two model proteins (one short, consisting of 124 residues and the other large, consisting of 2500 residues) demonstrate that the hydrogen bond networks play a very important role in the protein folding/unfolding phenomena.
Keywords: Hydrogen bonding; Protein folding; Protein denaturation; Mean first passage time; Nucleation mechanism; Barrierless unfolding;

The liquid interface around an adsorbed colloidal particle can be undulated because of roughness or heterogeneity of the particle surface, or due to the fact that the particle has non-spherical (e.g. ellipsoidal or polyhedral) shape. In such case, the meniscus around the particle can be expanded in Fourier series, which is equivalent to a superposition of capillary multipoles, viz. capillary charges, dipoles, quadrupoles, etc. The capillary multipoles attract a growing interest because their interactions have been found to influence the self-assembly of particles at liquid interfaces, as well as the interfacial rheology and the properties of particle-stabilized emulsions and foams. As a rule, the interfacial deformation in the middle between two adsorbed colloidal particles is small. This fact is utilized for derivation of accurate asymptotic expressions for calculating the capillary forces by integration in the midplane, where the Young–Laplace equation can be linearized and the superposition approximation can be applied. Thus, we derived a general integral expression for the capillary force, which was further applied to obtain convenient asymptotic formulas for the force and energy of interaction between capillary multipoles of arbitrary orders. The new analytical expressions have a wider range of validity in comparison with the previously published ones. They are applicable not only for interparticle distances that are much smaller than the capillary length, but also for distances that are comparable or greater than the capillary length.
Keywords: Particles at liquid interfaces; Lateral capillary interactions; Forces between capillary multipoles;