Grazing incidence X-ray diffraction studies of condensed double-chain phospholipid monolayers formed at the soft air/water interface

The use of highly brilliant synchrotron light sources in the middle of the 1980s for X-ray diffraction has revolutionized the research of condensed monolayers. Since then, monolayers gained popularity as convenient quasi two-dimensional model systems widely used in biophysics and material science. This review focuses on structures observed in one-component phospholipid monolayers used as simplified two-dimensional models of biological membranes. In a monolayer system the phase transitions can be easily triggered at constant temperature by increasing the packing density of the lipids by compression. Simultaneously the monolayer structure changes are followed in situ by grazing incidence X-ray diffraction. Competing interactions between the different parts of the molecule are responsible for the different monolayer structures. These forces can be modified by chemical variations of the hydrophobic chain region, of the hydrophilic head group region or of the interfacial region between chains and head groups. Modifications of monolayer structures triggered by changes of the chemical structure of double-chain phospholipids are highlighted in this paper.     

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.     

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.     

Surface viscoelasticity of phospholipid monolayers at the air/water interface

The surface viscoelastic properties of monolayers of two phospholipids DPPC (L--dipalmitoylphosphatidylcholine) and DMPE (L--dimyristoylphosphatidyl-ethanolamin), at the air-water interface have been investigated. Two techniques were used for the investigation. One involved use of an interfacial shear rheometer (torsion pendulum apparatus ISR1), to provide measurements of the shear viscosity _s as a function of surface pressure, and the second, a modified LB trough with an oscillating barrier to generate periodie dilation and compression so as to measure the dilational elastic modulusE as a function of surface area.Results indicate a strong dependence of _s andE upon monolayer phases. This suggests that the viscoelastic relaxation of monolayers can be understood as molecular rearrangements, domain exchange and molecular reorientations between different monolayer states.     

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.     

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.     

Anomalous spreading behaviour of polyethyleneglycoldistearate monolayers at air/water interface

Spreading behaviour of the dimeric surfactant polyethylene-glycoldistearate (PEGDS) monolayer at air/water interface has been studied using surface pressure-area (π-A) isotherms as a function of temperature. The isotherms show a plateau suggesting a transition between a liquid expanded (LE) and a condensed state. The condensed state possibly arises due to nucleation and growth of multilayers from the monolayer. Isobaric measurements of bothA-T and π-T at constant area show transitions atT = 295 K. These plots suggest a melting followed by formation of condensed microcrystallites. Structure optimization carried out using various angles of orientation of the alkyl tails with respect to the backbone in PEGDS reveals tilt transitions of the tails in different states which can be related to the packing behaviour seen in the isotherms. Optical microscopy has been used to confirm the structures in these states.     

Miscibility of mixed stereoregular PMMA/PVPh monolayers at the air/water interface

The mixed monolayer behavior of stereoregular poly(methyl methacrylate) (PMMA) and poly(vinyl phenol) (PVPh) was investigated from the measurements of surface pressure–area per molecule (π–A) isotherms. The π–A isotherms indicated that isotactic PMMA (iPMMA) and PVPh were miscible at the air/water interface. The miscibility and non-ideality of the mixed monolayers were examined by calculating the excess area as a function of composition, and negative deviations from ideality were observed, which suggest the existence of attractive interactions between iPMMA and PVPh. However, the π–A isotherms of mixed syndiotactic PMMA (sPMMA)/PVPh monolayers showed positive deviation from ideality, which might suggest that non-favorable interactions exist between sPMMA and PVPh.The π–A isotherms of mixed atactic PMMA (aPMMA)/PVPh monolayers exhibited complicated excess area behavior. Both positive and negative deviations from ideality were observed at various surface pressures. These isotherm results of mixed polymers correlate approximately well with the miscibility of the corresponding mixtures in the bulk state. The formation of hydrogen bonding between PMMA and PVPh was substantiated in the bulk state by means of Fourier transform infrared (FTIR). Regardless of tacticity, an increase of hydrogen-bonded carbonyl fraction was observed.     

Long-range nanometer-scale organization of semifluorinated alkane monolayers at the air/water interface

We have determined the structure formed at the air-water interface by semifluorinated alkanes (C(8)F(17)C(m)H(2m+1) diblocks, F8Hm for short) for different lengths of the molecule (m = 14, 16, 18, 20) by using surface pressure versus area per molecule isotherms, Brewster angle microscopy (BAM), and grazing incidence x-ray experiments (GISAXS and GIXD). The behavior of the monolayers of diblocks under compression is mainly characterized by a phase transition from a low-density phase to a condensed phase. The nonzero surface pressure phase is crystalline and exhibits two hexagonal lattices at two different scales: a long-range-order lattice of a few tens of nanometers lateral parameter and a molecular array of about 0.6 nm parameter. The extent of this organization is sufficiently large to impact larger scale behavior. Analysis of the various compressibilities evidences the presence of non organized molecules in the monolayer for all 2D pressures. At room temperature, the self-assembled structure appears generic for all the F8Hm investigated.     

Lateral quantized charge transfer across nanoparticle monolayers at the air/water interface

Lateral quantized charge transfer was observed with gold nanoparticle monolayers at the air/water interface. The electronic conductivity was measured by using an interdigitated arrays (IDA) electrode perpendicularly aligned at the air/water interface where a particle ensemble was trapped between the IDA fingers. The overall voltammetric responses were analogous to that of the Coulomb blockade with a relatively flat central gap. This gap was found to shrink with increasing surface pressure. Differential pulse voltammetry revealed a series of well-defined voltammetric peaks within this central gap, which are ascribed to the single electron transfer of the particle ensemble. This observation was interpreted on the basis of relatively weak electronic coupling between neighboring particles where the particles behave more individually.     

Competition between atmospherically relevant fatty acid monolayers at the air/water interface

Competition and oxidation of fatty acids spread at the air/water interface were investigated using surface-specific, broad-bandwidth, sum frequency generation spectroscopy. At the air/water interface, a monolayer of oleic acid replaced a monolayer of deuterated palmitic acid at equilibrium spreading pressure. Subsequent oxidation of the oleic acid monolayer with ozone resulted in products more water soluble than the palmitic acid; therefore, the palmitic acid monolayer reformed at the surface. Results indicate that the surfactants on the surface of fat-coated tropospheric aerosols will only possess oxidized acyl chains after all less soluble species in the aqueous subphase have been removed through the processes of replacement at the surface and atmospheric oxidation.     

Interactions between phosphatidylcholines and cholesterol in monolayers at the air/water interface

Mixtures of cholesterol and synthetic phospholipids, differing in saturation of phosphatidylcholine (PC) acyl chains, such as distearoyl phosphatidylcholine (DSPC), stearoyl-oleoyl phosphatidylcholine (SOPC) and dioleoyl phosphatidylcholine (DOPC) have been studied as floating Langmuir monolayers at the air/water interface. In order to examine the influence of a polar group, distearoyl phosphatidylethanolamine (DSPE) was chosen. The films were spread at room temperature on aqueous subphases and characterized by the surface pressure-area (pi-A) isotherms and compression modulus (C(s)(-1)) values. The interactions were examined by analyzing the mean molecular areas and quantified by the excess free energy of mixing values. The obtained results indicate that the affinity of cholesterol to saturated/unsaturated phosphatidylcholines does not differ significantly, and revealed strong influence of the kind of a polar group on the cholesterol-phospholipid interactions. On the other hand, the apolar group structure was found to modify the stoichiometry of sterol-PC complexes.     

Catalase monolayers at the air/water interface I. Reversibilities and irreversibilities

/A-isotherms of catalase monolayers established at the air/water-interface are discussed quantitatively on the basis of molecular data: A relationship between a critical value of the surface pressure, the corresponding molecular area, and the molecular dimension of the molecules at the interface is proposed. It is shown that the unfolding of molecules at the water surface is pH-dependent. For each pH-value there is a distinct degree of unfolding; the molecules keep their globular state at neutral pH. Establishment at the surface of bulk solutions corresponding to globular and partly unfolded states, respectively, catalase molecules keep their original configuration on changing the pH-value of bulk-phase. The monolayers are confirmed to show reversibility with regard to lateral changes of state as well as irreversibility with respect to desorption of molecules.A model is proposed to explain the nature of the critical/A-value occurring in the/A-isotherms: on compression beyond _c, molecular segments are transferred from the surface into the bulkphase via a subsurface layer. From the experiments it is concluded that the surface pressure is determined, not only by the surface itself, but also by this subsurface layer.     

Nanoplates and nanostars of β-PbO formed at the air/water interface

Nanoparticles with different shapes were prepared at the air/water interface via hydrolysis of Pb²⁺ ions under Langmuir films of poly(N-vinylcarbazole) (PVK) at 30–50 °C. It was found that round or irregular nanoparticles with the size of several to several tens of nanometers were formed when the PbCl₂ aqueous solution with the concentration of 1 × 10^?3 mol L^?1 was used as subphase, while single-crystalline quasi-hexagonal nanoplates, nanostars and dendrites with the size of several hundreds of nanometers were obtained when the subphase concentration was 1 × 10^?4 mol L^?1. Analysis on the selective-area electron diffraction (SAED) patterns revealed that the formed nanoparticles are β-PbO. The formation of the nanostructures should be attributed to the formation and dehydration of lead hydroxide, diffuse-limited growth and aggregation of nanoparticles at the air/water interface.     

Mixed monolayers of Gemini surfactants and stearic acid at the air/water interface

The properties of mixed monolayers composed of the cationic Gemini surfactant ([C(18)H(37)(CH(3))(2)N(+)(CH(2))(3)N(+)(CH(3))(2)C(18)H(37)],2Br(+), abbreviated as 18-3-18,2Br(-1)) and stearic acid (SA) at the air/water interface were investigated by using a Langmuir film balance. The excess areas at the different mixed monolayer compositions were obtained and used to evaluate the miscibility and nonideality of mixing. Due to the electrostatic attractive interactions between 18-3-18,2Br(-1) and SA, the excess areas indicated negative deviations from ideal mixing. Moreover, 18-3-18,2Br(-1) and SA were miscible at the air/water interface, as was confirmed by atomic force microscopy (AFM) images of the LB films transferred onto mica substrates. The attenuated total reflectance (ATR) infrared spectra showed that SA in the mixed monolayers was ionized completely at a composition X(SA)=0.67 and formed a "cationic-anionic surfactant," i.e., the carboxylate, with 18-3-18,2Br(-1) owing to the electrostatic interaction between the head groups.     

Interaction of rabbit C-reactive protein with phospholipid monolayers at air/water interface

C-reactive protein (CRP) is a major acute phase reactant in most mammalian species. The structure of CRP has been previously established by crystallography, and the significance of its interaction with lipid membranes is accepted in the literature. However, the nature of the interaction between CRP and phospholipids is not yet well understood. In this paper we use monolayer technique to study the characteristics of the interaction of rabbit C-reactive protein (rCRP) with the phospholipid membranes. The results show that rCRP is surface active and can spontaneously insert into the lipid monolayers. The critical pressure for rCRP inserting into the phospholipid monolayers is about 34.5 mN/m, which is not sensitive to the types of the lipid headgroups and the presence of calcium ions in the subphase. The findings of this paper may provide a clue to the further understanding of the mechanism of the interactions between rCRP and the biological membranes.     

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.