Effect of the graft chain length and density on the morphology of radiation-modified polysilane monolayers at the air/water interface

The variation in the morphology of monolayers at the air/water interface is investigated for two kinds of radiation-modified polysilanes with different structures: poly(diethyl fumarate)-grafted poly(methyl-n-propylsilane) (PMPrS-g-PDEF) and maleic anhydride-grafted PMPrS (PMPrS-g-MAH). PMPrS-g-PDEF has long but sparsely-attached PDEF graft chains, while PMPrS-g-MAH has short but densely-attached MAH graft units. Surface pressure-area measurements indicate that PMPrS-g-PDEF monolayers extensively spread at the air/water interface though PMPrS homopolymer hardly spreads. AFM observation reveals that PMPrS-g-PDEF monolayers have an inhomogeneous structure containing string-like microstructures. This result suggests that PMPrS main chains are detached from the water surface to aggregate together and only PDEF chains spread over the water surface. In contrast, PMPrS-g-MAH forms uniform monolayers with a smooth surface. PMPrS main chains of PMPrS-g-MAH are anchored to the water surface by densely grafted MAH units. It is also demonstrated that only the PMPrS-g-MAH monolayers are successfully deposited layer-by-layer on a solid substrate by the Y-type deposition.     

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.     

Interaction of the neurotransmitter, neuropeptide Y, with phospholipid membranes: infrared spectroscopic characterization at the air/water interface

The association of neuropeptide Y (NPY) at the air/water interface and with phospholipid monolayers on water as subphase has been investigated using external infrared reflection absorption spectroscopy (IRRAS). Studies of the conformation and orientation of NPY suggest that it adopts an alpha-helical structure and is oriented parallel to the air/water interface in neat peptide monolayers. Both secondary structure and orientation are preserved in mixed lipid/NPY monolayers. Comparison of NPY associated with zwitterionic DPPC and with anionic DMPS suggests that electrostatic attraction plays a major role for peptide binding to the membrane surface.     

Self-assembly of amphiphilic hexapyridinium cations at the air/water interface and on HOPG surfaces.

Mono- and multilayers of a novel amphiphilic hexapyridinium cation with six eicosyl chains (3) are spread at the air/water interface as well as on highly ordered pyrolytic graphite (HOPG). On water, the monolayer of 3 is investigated by recording surface pressure/area and surface potential/area isotherms, and by Brewster angle microscopy (BAM). Self-organized tubular micelles with an internal edge-on orientation of molecules form at the air/water interface at low surface pressure whereas multilayers are present at high surface pressure, after a phase transition. Packing motifs suggesting a tubular arrangement of the constituting molecules were gleaned from atomic force microscopy (AFM) investigations of Langmuir-Blodgett (LB) monolayers being transferred on HOPG at different surface pressures. These LB film structures are compared to the self-assembled monolayer (SAM) of 3 formed via adsorption from a supersaturated solution, which is studied by scanning tunnelling microscopy (STM). On HOPG the SAM of 3 consists of nanorods with a highly ordered edge-on packing of the aromatic rings and an arrangement of alkyl chains which resembles the packing of molecules at the air/water interface at low surface pressure. Additional details of the molecular packing were gleaned from single-crystal X-ray structure analysis of the hexapyridinium model compound 2b, which possesses methyl instead of eicosyl residues.     

Micellization of PEO/PS block copolymers at the air/water interface: a simple model for predicting the size and aggregation number of circular surface micelles

Isotherms of monolayers of poly(ethylene oxide) (PEO) and polystyrene (PS) triblock copolymers spread at the air/water interface were obtained by film balance technique. In a low concentration regime, the PEO segments surrounding the PS cores behave the same way as in monolayers of PEO homopolymers. Langmuir-Blodgett (LB) films prepared by transferring the monolayers onto mica at various surface pressures were analyzed by atomic force microscopy (AFM). The results reveal that these block copolymers form micelles at the air/water interface. Within the micelles, the PS blocks act as anchoring structures at the interface. In several cases, aggregation patterns were modified by the dewetting processes that occur in Langmuir-Blodgett films transferred to solid substrates. High transfer surface pressures and metastable states favored these changes in morphology. A flowerlike surface micelle model is proposed to explain the organization of the surface circular micelles. The model can be generalized and applied to diblock copolymers as well. The model permits prediction of the aggregation number and the size of circular surface micelles formed by PEO/PS block copolymers at the air/water interface.     

Minimizing defects in polymer-based Langmuir-Blodgett monolayers and bilayers via gluing

Polymeric surfactants were prepared by quaternization of poly(4-chloromethylstyrene) with N,N-dimethyl-N-n-dodecylamine and N,N-dimethyl-N-n-octylamine to give 1 and 2, respectively. Each of these polymers formed stable monolayers at the air/water interface. Injection of poly(acrylic acid) (PAA) beneath the surface of these films led to a substantial increase in their cohesiveness (i.e., "gluing"), as evidenced by a dramatic increase in their surface viscosity. Examination of monolayers of 1 by atomic force microscopy, after being transferred to silicon wafers that were surface-modified with n-octadecyltrichlorosilane, showed that the presence of PAA leads to intact film. In contrast, transfer of unglued monolayers resulted in poor coverage. Comparison of the barrier properties of single glued and unglued LB bilayers formed in the presence and in the absence of PAA have shown that PAA minimizes defect formation within these ultrathin assemblies.     

Preparation and photophysical properties of thin films of coumarin dyes

The results from investigating the photophysical properties of new coumarin dyes synthesized and incorporated into Langmuir-Blodgett films are presented. A method for forming monolayers on the surface of a water/air interface is proposed. The phase states of mixed monolayers on a water surface are studied. It is found that mixed monolayers of amphiphilic polyampholyte and dye allow us to obtain more stable and condensed films, relative to films of single components. The spectral and luminescent properties of synthesized dyes in solution and in Langmuir-Blodgett films are studied.     

Dangling OD confined in a Langmuir monolayer

Novel structural features of water confined in lipid Langmuir monolayers are revealed. Using vibrational sum frequency generation spectroscopy at the air/D2O/monolayer interface, dangling OD bonds were investigated. Upon increasing the monolayer surface coverage, the dangling OD stretching mode showed a marked frequency red-shift as well as spectral structure. Furthermore, the dangling OD was found to exist even when a D2O surface was fully covered by the lipid molecules. This phenomenon was observed in monolayers formed with dipalmitoylphosphatidylcholine and with palmitic acid. The frequency red-shift of the dangling OD is interpreted to be due to the perturbation imposed by the lipid hydrophobic tail groups. The observed persistence of the dangling OD at full surface coverage is related to hydrophobicity-induced drying.     

A straightforward way to form close-packed TiO2 particle monolayers at an air/water interface

The aim of this study was to analyze if and how monolayers of TiO(2) particles could be directly formed at the air/water interface and if these monolayers could be transferred to a solid surface. TiO(2) particles with diameters of 300 nm, 500 nm, 1 μm, 5 μm, 10 μm, and 20 μm formed stable monolayers at pH 2. At low surface pressures, the particles formed small two-dimensional aggregates. Particles up to a radius of 5 μm displayed close packing at increased surface pressures. Particles of 10 μm radius formed a loose network, which is attributed to the strong adhesion caused by the weight-induced lateral capillary attraction. Every monolayer of particles could be transformed to a solid surface by the Langmuir-Blodgett deposition. At pH 6 or 11, the particles did not form stable monolayers at the air/water interface. They were instead dispersed in the aqueous phase and eventually sank to the bottom of the trough. At pH 11 the monolayer could, however, be stabilized by the addition of salt (0.5 M NaCl). The results are interpreted based on a changed wettability of the particles depending on pH and salt concentration.     

Rheology of poly(methyl methacrylate) Langmuir monolayers: percolation transition to a soft glasslike system

An experimental study of the equilibrium properties and of the surface rheology of Langmuir monolayers of poly(methyl methacrylate) (PMMA) at the air/water interface has been carried out as a function of polymer concentration (Γ) and molecular weight (M(w)). Dilational and shear complex elasticity moduli covering a frequency range from 10(-3) to 0.2 Hz have been discussed. It was found that the air∕water interface behaves as a poor solvent for PMMA monolayers, thus suggesting that the polymer coils take collapsed soft-disks (pancakes) shape at the interface. The equilibrium and dynamic results suggest a fluid-to-soft-glass transition as the polymer concentration increases above a critical packing fraction at constant temperature. This two-dimensional transition is in agreement with results previously discussed for the dilational rheology of poly(4-hydroxystyrene) [F. Monroy, F. Ortega, R. G. Rubio, H. Ritacco, and D. Langevin, J. Chem. Phys. 95, 056103 (2005)]. Furthermore, the Γ-dependence of the relaxation dynamics of the monolayers suggests that the gel state may be considered as a fragile soft glass.     

Spectroscopic studies of the stability of monolayers of 2-docosylamino-5-nitropyridine at the air/water interface

Monolayers of 2-docosylamino-5-nitropyridine (DCANP) at the air/water interface were investigated by UV/Vis spectroscopy. The combination of this method with the classic constant-area relaxation technique yields insight into the longtime stability and the collapse behavior of monolayers. We have demonstrated that monolayers of DCANP are certainly stable under standard deposition conditions. At surface pressures above 20 mN/m monolayer instabilities lead to the formation of a three-dimensional head-to-head multilayered structure.     

Evidence of strong hydration and significant tilt of amphiphilic [2]rotaxane molecules in Langmuir films studied by synchrotron X-ray reflectivity

Surface sensitive X-ray techniques have been used to elucidate the structures of amphiphilic [2]rotaxane and dumbbell monolayers at the air/water interface. The [2]rotaxanes were found to adopt highly hydrated tilted and/or folded conformations on the water surface largely due to the hydrophilic nature of their tetracationic ring component. This conformation was less pronounced in monolayers of the dumbbell precursors. Increasing the surface pressure resulted in an expansion of [2]rotaxane monolayers in the vertical direction and decreased hydration.     

Computer studies on the effects of long chain alcohols on sodium dodecyl sulfate (SDS) molecules in SDS/dodecanol and SDS/hexadecanol monolayers at the air/water interface

Molecular dynamics simulations of sodium dodecyl sulfate (SDS)/dodecanol and SDS/hexadecanol monolayers at the air/water interface were investigated where the monolayer mixtures were prepared by two different configurations. In the first configuration, all of the dodecanol (or hexadecanol) molecules were placed together and also the SDS molecules were placed together in the surface area. In the second configuration, the dodecanol (or hexadecanol) molecules were uniformly distributed with the SDS molecules, forming a homogeneous mixture. The results showed that the alcohol tails are more ordered and thicker than the SDS tails in monolayers where the alcohol molecules are close to each other and separated from the SDS. However, the reverse trend is observed in monolayers where the SDS and alcohol molecules are well mixed; that is, the alcohol tails seem to have less order. Studies of how the SDS tails are affected by the presence of long chain alcohols are also discussed. Basically, by increasing the alcohol chain length, the order and the thickness of the SDS tails increased when those molecules were placed all together in a region of the surface area. When both surfactants were well mixed, the order and thickness of the SDS chains decreased as the alcohol chain length increased. Comparisons of the present results with actual experiments of similar systems were performed, and they showed similar tendencies.     

Ordering effects of cholesterol on sphingomyelin monolayers investigated by high-resolution broadband sum-frequency generation vibrational spectroscopy

After adding cholesterol, the sphingosine backbones (red) of the three nature SMs become more ordered, and the N-linked acyl chain (blue) remains unaltered.     

Fatty-acid monolayers at the nematic/water interface: phases and liquid-crystal alignment

The two-dimensional (2D) phases of fatty-acid monolayers (hexadecanoic, octadecanoic, eicosanoic, and docosanoic acids) have been studied at the interface of a nematic liquid crystal (LC) and water. When observed between crossed polarizers, the LC responds to monolayer structure owing to mesoscopic alignment of the LC by the adsorbed molecules. Similar to Langmuir monolayers at the air/water interface, the adsorbed monolayer at the nematic/water interface displays distinct thermodynamic phases. Observed are a 2D gas, isotropic liquid, and two condensed mesophases, each with a characteristic anchoring of the LC zenithal tilt and azimuth. By varying the monolayer temperature and surface concentration we observe reversible first-order phase transitions from vapor to liquid and from liquid to condensed. A temperature-dependent transition between two condensed phases appears to be a reversible swiveling transition in the tilt azimuth of the monolayer. Similar to monolayers at the air/water interface, the temperature of the gas/liquid/condensed triple-point temperature increased by about 10 degrees C for a two methylene group increase in chain length. However, the absolute value of the triple-point temperatures are depressed by about 40 degrees C compared to those of analogous monolayers at the air/water interface. We also observe a direct influence by the LC layer on the mesoscopic and macroscopic structure of the monolayer by analyzing the shapes and internal textures of gas domains in coexistence with a 2D liquid. An effective anisotropic line tension arises from elastic forces owing to deformation of the nematic director across phase boundaries. This results in the deformation of the domain from circular to elongated, with a distinct singularity. The LC elastic energy also gives rise to transition zones displaying mesoscopic realignment of the director tilt or azimuth between adjacent regions with a sudden change in anchoring.     

Wetting in oil/water/surfactant systems

The behaviour of oils at aqueous interfaces is ubiquitous to many industrially and biologically relevant processes. In this review we consider modifications to the wetting properties of oils at the air/water, oil/water and solid/liquid interfaces in the presence of surfactants. First-order wetting transitions can be induced in a wide range of oils by varying the aqueous surfactant concentration, leading to the formation of mixed monolayers at the interface. In certain cases, these mixed monolayers display novel surface freezing behaviour, including the formation of unusual bilayer structures, which further modifies the properties of the interface. The effects of surfactant on line tension at the three-phase contact line and differences between the air/liquid and liquid/liquid interfaces are discussed.     

Recent developments in the modeling of the monolayers structure at the water/air interface

Different models recently used to characterize adsorbed and Langmuir monolayers at the water/air interface are reviewed in this paper. Methods for the determination of the orientation of molecules at the surface are described and compared.     

Orientation,recognition, and photoreaction of nucleolipids in model membranes

Amphiphiles with nucleobases and nucleosides as headgroups have been synthesized. Their surface behavior was investigated in monolayers at the air/water interface. The double chain nucleolipids form stable monolayers with nearly identical surface pressure-area diagrams, whereas the spreading behavior of the mono chain amphiphiles is dominated by the various nucleobase-headgroups. When measuring the interactions between nucleolipid monolayers and nucleobases (monomeric and polymeric ones), specific base-base effects could be observed: the complementary nucleobases solubilized in the subphase expand the monolayer more than the non-complementary ones. Photodimerization reactions of thymine-amphiphiles were investigated in mono- and multilayers as well as in spin-coated films.