Fluid Monolayer Research Articles

Adsorption model and phase transitions of diblock perfluoroalkylated surfactants at the water∣alkane interface

We present a theory of the adsorption behaviour and phase transitions in monolayers of perfluoroalkylated alcohols, n-CnF2n+1CmH2mOH, at the water∣oil interface, and validate it for a range of temperatures and surfactant structures. The reason for the observed cohesive behaviour is identified as dispersion attraction between the fluorocarbon blocks. The London constant is determined from the increment of the lateral attraction parameter with the size of the fluorocarbon chain. The monolayers exhibit phase transition from liquid expanded state to van der Waals crystal. However, they are supercritical with respect to the gas–liquid transition. For the description of the liquid phase, we use the sticky disc model – fluid monolayer made of hard discs interacting with a short-ranged sticky potential. For the crystalline phase, a two-dimensional cell model is developed using the same interaction potential. This new model coincides with the empirical equation of state of Jura and Harkins, and ascribes physical meaning to its parameters. We extend the theory of Ivanov et al. for the adsorption constant Ka to diblock molecules; it predicts accurately the dependence of Ka and the adsorption heat on the surfactant structure. An invariant phase diagram of the monolayers is constructed.

Membrane properties of ether-type phosphatidylcholine bearing partially fluorinated C18-monoacetylenic chains and their applicability to membrane protein reconstitution matrices

To examine the applicability of fluorinated membrane-forming phospholipids to reconstitution matrices for functional membrane proteins, the membrane properties of a synthetic ether-type phosphatidylcholine (PC) bearing partially fluorinated C18-monoacetylenic (9-octadecynyl) chains, DF8CCH8PC, were compared with those of its non-fluorinated counterpart, DH8CCH8PC. Light-harvesting complex 2 (LH2) and the light-harvesting 1‒reaction center core complex (LH1-RC) isolated from purple photosynthetic bacteria were employed as probe membrane proteins to evaluate the extent to which their reconstitution into DF8CCH8PC membranes could proceed. DF8CCH8PC formed more expanded and more stable fluid monolayers than DH8CCH8PC at the air-water interface at 25 °C; the former PC molecule occupied an area of ca. 0.70 nm2 at a collapse pressure, πc, of 52 mN/m, while the latter occupied an area of ca. 0.55 nm2 at a πc of 45 mN/m. In contrast, the molecular motion detected using fluorescent probes was much more restricted in DF8CCH8PC bilayers than in DH8CCH8PC ones. Although the reconstitution efficiencies of both LH2 and LH1-RC into DF8CCH8PC bilayers were lower than those into DH8CCH8PC bilayers, the membrane proteins incorporated into DF8CCH8PC bilayers showed increased thermostability. The increased thermostability of these proteins in fluorinated PC membranes might be due to the restricted molecular motion in the hydrophobic chains. The results of this study suggest that partially fluorinated PCs can be useful materials for the construction of lipid‒functional membrane protein assemblies including large membrane protein complexes, such as LH1-RC, for biotechnological applications.

Effect of Mineral-Oil Addition on Film Stability of Polar Lipid Constituents Derived from Meibum.

We studied the effects of mineral oil (MO) on the properties and structure of a spread monolayer of polar lipid constituents in meibum, by performing cyclic lateral compression-expansion experiments using a Langmuir trough. A meibum sample without nonpolar lipids (meibumΔnonpolar-lipid) was prepared by removing the nonpolar lipids from biological meibum extruded from rabbit eyelids and spread on a water surface for measuring the cyclic surface pressure (π)-film area (A) isotherms with in situ observation of the film morphology using a Brewster angle microscope. The meibumΔnonpolar-lipid formed a homogeneous fluid monolayer and underwent collapse upon compression. The π-A isotherm shifted to a smaller area upon repeating the compression-expansion cycles. These observations contrasted those obtained for meibum previously, which may have resulted from the absence of nonpolar lipids. The recovery of the film stability against the lateral compression-expansion cycles was analyzed by adding MO as a nonpolar compound to the film system. A spread film of 1:1 mixture (by weight) could recover the high reversibility of the π-A isotherms during the repeated compression and expansion processes.

Thermoacoustic Instability in Two-Dimensional Fluid Complex Plasmas.

Thermoacoustic instability in a fluid monolayer complex plasma is studied for the first time. Experiments, theory, and simulations demonstrate that nonreciprocal effective interactions between particles (mediated by plasma flows) provide positive thermal feedback leading to acoustic sound amplification. The form of the generated sound spectra obtained both in experiments and simulations excellently agrees with theory, justifying thermoacoustic instability in the fluid complex plasma. The results indicate a physical analogy between collective fluctuation dynamics in reactive media and in systems with nonreciprocal effective interactions exposing an activation behavior.

Synthesis, characterization, and interactions of single-walled carbon nanotubes modified with doxorubicin with Langmuir\u2013Blodgett biomimetic membranes

The synthesis, characterization, and the influence of single-walled carbon nanotubes (SWCNTs) modified with an anticancer drug doxorubicin (DOx) on the properties of model biological membrane as well as the comparison of the two modes of modification has been presented. The drug was covalently attached to the nanotubes either preferentially on the sides or at the ends of the nanotubes by the formation of hydrazone bond. The efficiency of the modification was proved by the results of FTIR, Raman, and thermogravimetric analysis. In order to characterize the influence of SWCNT-DOx conjugates on model biological membranes, Langmuir technique has been employed. The mixed monolayers composed of 1,2-dipalmitoyl-sn-glycero-3-phosphothioethanol (DPPTE) and SWCNT-DOx with different weight ratio have been prepared. It has been shown that changes in the isotherm characteristics depend on the SWCNTs content. While smaller amounts of SWCNTs do not exert significant differences, the introduction of the prevailing content of the nanotubes increases area per molecule and decreases the maximum value of compression modulus, leading to more fluid monolayer. However, upon increasing the surface pressure, the aggregation of carbon nanotubes within the thiolipid matrix has been observed. Mixed layers of DPPTE/SWCNT-DOx were also transferred onto gold electrodes by means of LB method. Cyclic voltammetry showed that SWCNT-DOx conjugates remain adsorbed at the electrode surface and are stable in time. Additionally, higher values of peak current and DOx surface concentration obtained for side modification prove that side modification allows for more efficient conjugation of the drug to carbon nanotubes.Graphical abstractᅟ

Effects of Aggregate Charge and Subphase Ionic Strength on the Properties of Spread Polyelectrolyte/Surfactant Films at the Air/Water Interface under Static and Dynamic Conditions.

We demonstrate the ability to tune the formation of extended structures in films of poly(sodium styrenesulfonate)/dodecyltrimethylammonium bromide at the air/water interface through control over the charge/structure of aggregates as well as the ionic strength of the subphase. Our methodology to prepare loaded polyelectrolyte/surfactant films from self-assembled liquid crystalline aggregates exploits their fast dissociation and Marangoni spreading of material upon contact with an aqueous subphase. This process is proposed as a potential new route to prepare cheap biocompatible films for transfer applications. We show that films spread on water from swollen aggregates of low/negative charge have 1:1 charge binding and can be compressed only to a monolayer, beyond which material is lost to the bulk. For films spread on water from compact aggregates of positive charge, however, extended structures of the two components are created upon spreading or upon compression of the film beyond a monolayer. The application of ellipsometry, Brewster angle microscopy, and neutron reflectometry as well as measurements of surface pressure isotherms allow us to reason that formation of extended structures is activated by aggregates embedded in the film. The situation upon spreading on 0.1 M NaCl is different as there is a high concentration of small ions that stabilize loops of the polyelectrolyte upon film compression, yet extended structures of both components are only transient. Analogy of the controlled formation of extended structures in fluid monolayers is made to reservoir dynamics in lung surfactant. The work opens up the possibility to control such film dynamics in related systems through the rational design of particles in the future.

Lysine-based amino-functionalized lipids for gene transfection: the influence of the chain composition on 2D properties.

The influence of the chain composition on the physical-chemical properties will be discussed for five transfection lipids containing the same lysine-based head group. For this purpose, the chain composition will be gradually varied from saturated tetradecyl (C14:0) and hexadecyl (C16:0) chains to longer but unsaturated oleyl (C18:1) chains with double bonds in the cis configuration. In this work, we investigated the lipids as Langmuir monolayers at the air-water-interface in the absence and presence of calf thymus DNA applying different techniques such as infrared reflection absorption spectroscopy (IRRAS) and grazing incidence X-ray diffraction (GIXD). The replacement of saturated tetradecyl (C14:0) and hexadecyl (C16:0) chains by unsaturated oleyl (C18:1) chains increases the fluidity of the lipid monolayer: TH10 < TT10 < OH10 < OT10 < OO10 resulting in a smaller packing density. TH10 forms the stiffest and OO10 the most fluid monolayer in this structure-property study. OO10 has a higher protonation degree compared to the saturated lipids TT10 and TH10 as well as to the hybrids OT10 and OH10 because of a better accessibility of the amine groups. Depending on the bulk pH, different scenarios of DNA coupling to the lipid monolayers have been proposed.

Self assembly of cyclic polygon shaped fluid colloidal membranes through pinning.

2D fluid monolayer membranes of rod-like viruses spontaneously form in a mixture of rods and polymers through depletion attraction. The rods are uniformly oriented within the bulk and twist in a zone around the membrane edge. Surprisingly, we find that cyclic polygonal shaped colloidal membranes form when polymers are added to a mixture of long and short-thick rods with the long and short-thick rods forming the faceted core and lobes of the polygon, respectively. We demonstrate that the origin of this anisotropic shape lies in the phenomenon of spreading of one liquid over another in the presence of disorder. As a membrane of short-thick rods spreads over another of longer rods, the edge bound rods untwist to become part of the newly formed two-rod interface. However, a small fraction of rods fail to untwist as the two rod interface forms and act as mobile pinning centers. Capillary flow of short-thick rods drives all the pinning centers to a single location in the composite membrane which now acts like a junction. This pinning junction inhibits complete engulfing of one membrane by the other. Repeated sequential events like this then lead to formation of multiple junctions and the overall cyclic polygon topology. We find that pinning junctions are weakly cross-linked in nature instead of being topological defects. We outline the necessary and sufficient constraints on the nature of rods to obtain stable out of equilibrium cyclic polygon membranes. Our results show a unique counter-intuitive scenario where defects lead to self-assembly of ordered structures.

Interaction of DNA with Cationic Lipid Mixtures-Investigation at Langmuir Lipid Monolayers.

Four different binary lipid mixtures composed of a cationic lipid and the zwitterionic colipids DOPE or DPPC, which show different DNA transfer activities in cell culture models, were investigated at the soft air/water interface to identify transfection efficiency determining characteristics. Langmuir films are useful models to investigate the interaction between DNA and lipid mixtures in a two-dimensional model system by using different surface sensitive techniques, namely, epifluorescence microscopy and infrared reflection-absorption spectroscopy. Especially, the effect of adsorbed DNA on the properties of the lipid mixtures has been examined. Distinct differences between the lipid composites were found which are caused by the different colipids of the mixtures. DOPE containing lipid mixtures form fluid monolayers with a uniform distribution of the fluorescent probe in the presence and absence of DNA at physiologically relevant surface pressures. Only at high nonphysiological pressures, the lipid monolayer collapses and phase separation was observed if DNA was present in the subphase. In contrast, DPPC containing lipid mixtures show domains in the liquid condensed phase state in the presence and absence of DNA in the subphase. The adsorption of DNA at the positively charged mixed lipid monolayer induces phase separation which is expressed in the morphology and the point of appearance of these domains.

Interfacial rheology of coexisting solid and fluid monolayers.

Biologically relevant monolayer and bilayer films often consist of micron-scale high viscosity domains in a continuous low viscosity matrix. Here we show that this morphology can cause the overall monolayer fluidity to vary by orders of magnitude over a limited range of monolayer compositions. Modeling the system as a two-dimensional suspension in analogy with classic three-dimensional suspensions of hard spheres in a liquid solvent explains the rheological data with no adjustable parameters. In monolayers with ordered, highly viscous domains dispersed in a continuous low viscosity matrix, the surface viscosity increases as a power law with the area fraction of viscous domains. Changing the phase of the continuous matrix from a disordered fluid phase to a more ordered, condensed phase dramatically changes the overall monolayer viscosity. Small changes in the domain density and/or continuous matrix composition can alter the monolayer viscosity by orders of magnitude.

Effects of smooth random surface on fluid monolayer thermodynamics

We consider the lattice gas approach to statistical mechanics of fluid adsorbed on random surfaces with fluid-fluid and fluid-surface potentials. It was shown that effective Hamiltonian contains quenched random interactions and random site fields. Their statistical features combine the properties of random geometry and fluid-fluid pair interaction potential. The high-temperature expansion leads to infinite-ranged random field model and Sherrington–Kirkpatrick spin-glass model. Thermodynamic properties are evaluated using replica theory procedure widely used to analyze quenched disorder systems. On the other hand we consider the random field model in random graph with finite connectivity instead of previous “infinite-ranged” approximations. This model has been investigated using finite connectivity technique. The replica symmetry ansatz for the order function is expressed in terms of an effective-field distribution. Analysis of random geometry effects on thermodynamic properties in such approach was done for the first time.

Binding of the Cationic Peptide (KL)4K to Lipid Monolayers at the Air-Water Interface: Effect of Lipid Headgroup Charge, Acyl Chain Length, and Acyl Chain Saturation.

The binding of the cationic peptide (KL)4K to monolayers of different anionic lipids was determined by adsorption experiments. The chemical structure of the anionic phospholipids was changed in different ways. First, the hydrophobic region of phosphatidylglycerols was altered by elongation of the acyl chain length. Second, an unsaturated chain was introduced. Third, lipids with negatively charged headgroups of different chemical structure were compared. (KL)4K itself shows no surface activity and does not bind to monolayers of zwitterionic lipids. Analysis of (KL)4K binding to anionic lipid monolayers reveals a competition between two binding processes: (i) incorporation of the peptide into the acyl chain region (surface pressure increase) and (ii) electrostatic interaction screening the negative charges with reduction of charge repulsion (surface pressure decrease due to monolayer condensation). The lipid acyl chain length and the chemical structure of the headgroup have minor effects on the binding properties. However, a strong dependence on the phase state of the monolayer was observed. In the liquid-expanded (LE) phase, the fluid monolayer provides enough space, so that peptide insertion due to hydrophobic interactions dominates. For monolayers in the liquid-condensed (LC) phase, peptide binding followed by monolayer condensation is the main effect.

Magnetic microwire probes for the magnetic rod interfacial stress rheometer.

The magnetic needle interfacial shear rheometer is a valuable tool for the study of the mechanical properties of thin fluid films or monolayers. However, it is difficult to differentiate the interfacial and subphase contributions to the drag on the needle. In principle, the problem can be addressed by decreasing the needle diameter, which decreases the bulk contribution while the interfacial contribution remains essentially the same. Here we show the results obtained when using a new type of needle, that of magnetic microwires with diameter approximately 10 times thinner than for commercial needles. We show that the lower inertia of the microwires calls for a new calibration procedure. We propose such a new calibration procedure based on the flow field solution around the needle introduced in refs 1 and 2. By measuring thin silicone oil films with well-controlled interfacial viscosities as well as eicosanol (C20) and pentadecanoic acid (PDA, C15) Langmuir monolayers, we show that the new calibration method works well for standard needles as well as for the microwire probes. Moreover, we show that the analysis of the force terms contributing to the force on the needle helps to ascertain whether the measurements obtained are reliable for given surface shear viscosity values. We also show that the microwire probes have at least a 10-fold-lower resolution limit, allowing one to measure interfacial viscosities as low as 10(-7) N·m/s.

Anti‐evaporative mechanism of wax esters: implications for the function of tear fluid

AbstractPurpose Our aim was to explain the molecular level basis of the ability of wax ester (WE) films to retard evaporation close to their bulk melting temperature. We studied the surface behavior of behenyl palmitoleate (BP), a WE representing the most abundant meibum WEs.Methods Isotherm and isochor measurements coupled with imaging by Brewster angle microscopy (BAM) were used to study BP films at the air‐water interface. In addition, evaporation rates through BP films were measured.Results Close to room temperature, BP formed solid, non‐spreading islands when applied to the air‐water interface. Between 35 and 38 °C, a fluid, effectively spreading monolayer phase coexisted with solid domains of BP. At higher temperatures, BP formed completely fluid films. Mean molecular areas of the fluid and solid films were determined to be approximately 50 Å2 and 18 Å2, respectively. The thickness of a solid BP monolayer was determined to be 42 ± 6 Å by BAM measurements. A fluid BP monolayer only had minimal evaporation resistance, while a solid monolayer retarded evaporation by &gt; 50%.Conclusion Below 35 °C, BP assumes an extended conformation at the air‐water interface, similar to the bulk crystal structure of WEs. The extended conformation allows tight packing of hydrocarbon chains, which hinders the permeation of water molecules and leads to the evaporation retarding effect. Although the solid islands effectively retard evaporation, they do not spread at low temperatures and water evaporation proceeds through the uncovered areas of the surface. Coexistence of fluid and solid monolayer phases between 35 and 38 °C allows the film to spread, leading to a complete coverage of the interface by the solid phase and effective evaporation retardation.

Antievaporative mechanism of wax esters: implications for the function of tear fluid.

The tear film lipid layer (TFLL) is considered to act as an evaporation barrier and to maintain the tear film intact between blinks. In vitro methods have, however, failed to reproduce this evaporation-retarding effect. Wax esters (WEs) are a major component of the TFLL. Close to their bulk melting temperature, WEs have been found to retard the evaporation of water, but the nature of this mechanism has remained unclear. We studied the interfacial organization of WE films by measuring their isochors and isotherms and evaporation-retarding effect, and we imaged these films by Brewster angle microscopy (BAM). Behenyl palmitoleate (BP) was used as a representative WE because it resembles the WEs found in meibum. At low temperatures, BP forms solid monolayer crystals in which the molecules are organized in a bulk-like extended conformation. Within approximately 3 °C below the bulk melting temperature, these solid monolayer domains coexist with a fluid monolayer film. At temperatures above the bulk melting temperature, BP forms a completely fluid monolayer in which the molecules are in a hairpin conformation. A fluid hairpin monolayer of BP does not significantly retard evaporation, whereas a solid monolayer decreases evaporation by >50%. The results provide a molecular-level rationale for the evaporation-retarding properties of WEs close to their melting temperature.

Electron Transfer through 3D Monolayers on Au25 Clusters

The monolayer protecting small gold nanoparticles (monolayer-protected clusters, MPCs) is generally represented as the 3D equivalent of 2D self-assembled monolayers (SAMs) on extended gold surfaces. However, despite the growing relevance of MPCs in important applied areas, such as catalysis and nanomedicine, our knowledge of the structure of 3D SAMs in solution is still extremely limited. We prepared a large series of monodisperse Au25(SCnH2n+1)18 clusters (n=2, 4, 6, 8, 10, 12, 14, 16, 18) and studied how electrons tunnel through these monolayers. Electron transfer results, nicely supported by 1H NMR spectroscopy, IR absorption spectroscopy, and molecular dynamics results, show that there is a critical ligand length marking the transition between short ligands, which form a quite fluid monolayer structure, and longer alkyl chains, which self-organize into bundles. At variance with the truly protecting 2D SAMs, efficient electronic communication of the Au25 core with the outer environment is thus possible even for long alkyl chains. These conclusions provide a different picture of how an ultrasmall gold core talks with the environment through/with its protecting but not-so-shielding monolayer.

The Effect of Ectoins on the Structural Organization of the Tear Fluid Monolayer

We investigate the influence of Ectoin on the structural organization of the natural and artificial tear fluid lipid layers (ATFLL) using surface activity analysis and topographical studies. The natural meibomian lipids exhibit a continuous pressure-area isotherm without any phase transitions. In the presence of ectoin, the isotherm is expanded towards higher area per molecule implying decreased interaction between the lipid molecules. The AFM scans show presence of fiber like structures in the natural meibomian lipid film. In the presence of ectoine, droplet-like structures are observed which are hypothesized to be triacyl glycerols excluded from the lipid film. ATFLL illustrate the fluidizing effect of ectoine on the lipid films where the pressure-area isotherms are expanded in the presence of ectoin. With the addition of a triacyl glycerol to the mixture of DPPC and Chol-Palmitate, we observed the formation of similar drop-like structures in the presence of ectoine as in the case of natural meibomian lipid films. Consequently, the hypothesis explaining the exclusion of tri/di acyl glycerol from the meibomian lipid film in the presence of ectoine in the subphase is confirmed which lead us to a model describing the fluidizing effect of ectoine on meibomian lipid films.

Competition for space between a protein and lipid monolayers

Competitive adsorption is a general problem both in polymer and in biological systems. The equilibrium composition at a surface in contact either with polymer solutions or biological fluids depends on the competition between all the surface active material present in the medium. Such competition is particularly important in cell membranes where membrane proteins generated on ribosomes have to incorporate in the cell. Here we use fluovideo microscopy to study the competition for adsorption at the air/water interface between the enzyme glucose oxidase (GOx) and fluid monolayers of pentadecanoic acid (PDA). Although water soluble, GOx has a strong affinity for the air/water interface. We show that under certain conditions it inserts in the monolayer and causes a contraction of the Langmuir film and the formation of condensed domains. When exposed to a heterogeneous surface it is inserted in the less dense regions. Its crystallization leads to the deformation of the condensed domains followed by the destruction of their initial shape. By compressing the layer the protein is not removed from the interface where it eventually forms three-dimensional structures.

The phospholipid monolayer associated with perilipin-enriched lipid droplets is a highly organized rigid membrane structure

The significance of lipid droplets (LD) in lipid metabolism, cell signaling, and membrane trafficking is increasingly recognized, yet the role of the LD phospholipid monolayer in LD protein targeting and function remains unknown. To begin to address this issue, two populations of LD were isolated by ConA sepharose affinity chromatography: 1) functionally active LD enriched in perilipin, caveolin-1, and several lipolytic proteins, including ATGL and HSL; and 2) LD enriched in ADRP and TIP47 that contained little to no lipase activity. Coimmunoprecipitation experiments confirmed the close association of caveolin and perilipin and lack of interaction between caveolin and ADRP, in keeping with the separation observed with the ConA procedure. The phospholipid monolayer structure was evaluated to reveal that the perilipin-enriched LD exhibited increased rigidity (less fluidity), as shown by increased cholesterol/phospholipid, Sat/Unsat, and Sat/MUFA ratios. These results were confirmed by DPH-TMA, NBD-cholesterol, and NBD-sphingomyelin fluorescence polarization studies. By structure and organization, the perilipin-enriched LD most closely resembled the adipocyte PM. In contrast, the ADRP/TIP47-enriched LD contained a more fluid monolayer membrane, reflecting decreased polarizations and lipid order based on phospholipid fatty acid analysis. Taken together, results indicate that perilipin and associated lipolytic enzymes target areas in the phospholipid monolayer that are highly organized and rigid, similar in structure to localized areas of the PM where cholesterol and fatty acid uptake and efflux occur.

Role of electrostatic interactions in two-dimensional self-assembly of tobacco mosaic viruses on cationic lipid monolayers

We explore two-dimensional self-assembly of tobacco mosaic viruses (TMVs) on a substrate-supported, fluid lipid monolayer by manipulating the electrostatic interactions, with specific focus on the effects of the cationic lipid concentration in the monolayer and the presence of Ca 2+ ions in the surrounding bulk solution. The TMV assemblies were characterized by grazing-incidence X-ray scattering and atomic force microscopy, and the inter-particle interaction quantified through X-ray scattering data analysis. In the absence of Ca 2+ ions, we found that higher charge densities on the lipid monolayer led to poorer in-plane order, which may be attributed to faster adsorption kinetics, due to the surface potential that increases with charge density. At the same time, higher lipid-charge densities also resulted in weaker repulsion between TMVs, due to partial screening of Coulomb repulsion by mobile cationic lipids in the monolayer. The lipid-charge dependence was diminished with increasing concentration of Ca 2+ ions, which also led to tighter packing of TMVs. The results indicate that Ca 2+ ions strengthen the screening of Coulomb repulsion between TMVs and consequently enhance the role of attractive forces. Control experiments involving Na + ions suggest that the attractive inter-TMV interaction has contributions from both the van der Waals force and the counter-ion-induced attraction that depends on ion valence.