Langmuir and Langmuir-Blodgett films of poly(ethylene oxide)-b-poly(epsilon-caprolactone) star-shaped block copolymers

Self-assembly of poly(ethylene oxide)-block-poly(epsilon-caprolactone) five-arm stars (PEO-b-PCL) was studied at the air/water (A/W) interface. The block copolymers consist of a hydrophilic PEO core with hydrophobic PCL chains at the star periphery. All the polymers have the same number of ethylene oxide repeat units (9 per arm), and the number of epsilon-caprolactone repeat units ranges from 0 to 18 per arm. The Langmuir monolayers were analyzed by surface pressure/mean molecular area isotherms, compression-expansion hysteresis experiments, and isobaric relaxation measurements, and the Langmuir-Blodgett (LB) films' morphologies were investigated by atomic force microscopy (AFM). PCL homopolymers crystallize directly at the A/W interface in a narrow surface pressure range (11-15 mN/m). In the same pressure region, the star-shaped block copolymers undergo a phase transition corresponding to the collapse and the crystallization of the PCL chains as shown by the presence of a pseudoplateau in the isotherms. The LB films were prepared by transferring the Langmuir monolayers onto mica substrates at various surface pressures. AFM imaging confirmed the formation of PCL crystals in the LB monolayers of the PCL homopolymers and of the copolymers, but also showed that the PCL segments can undergo additional crystallization after monolayer transfer during water evaporation. The PCL crystal morphologies were also strongly influenced by the surface pressure and by the PEO segments.     

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.     

Effect of hydrocarbon chain and pH on structural and topographical characteristics of phospholipid monolayers

Structural characteristics (structure, elasticity, topography, and film thickness) of dipalmitoyl phosphatidylcholine (DPPC) and dioleoyl phosphatidylcholine (DOPC) monolayers were determined at the air-water interface at 20 degrees C and pH values of 5, 7, and 9 by means of surface pressure (pi)-area (A) isotherms combined with Brewster angle microscopy (BAM) and atomic force microscopy (AFM). From the pi-A isotherms and the monolayer elasticity, we deduced that, during compression, DPPC monolayers present a structural polymorphism at the air-water interface, with the homogeneous liquid-expanded (LE) structure; the liquid-condensed structure (LC) showing film anisotropy and DPPC domains with heterogeneous structures; and, finally, a homogeneous structure when the close-packed film molecules were in the solid (S) structure at higher surface pressures. However, DOPC monolayers had a liquid-expanded (LE) structure under all experimental conditions, a consequence of weak molecular interactions because of the double bond of the hydrocarbon chain. DPPC and DOPC monolayer structures are practically the same at pH values of 5 and 7, but a more expanded structure in the monolayer with a lower elasticity was observed at pH 9. BAM and AFM images corroborate, at the microscopic and nanoscopic levels, respectively, the same structural polymorphism deduced from the pi-A isotherm for DPPC and the homogeneous structure for DOPC monolayers as a function of surface pressure and the aqueous-phase pH. The results also corroborate that the structural characteristics and topography of phospholipids (DPPC and DOPC) are highly dependent on the presence of a double bond in the hydrocarbon chain.     

Flexibility of the triblock copolymers modulating their penetration and expulsion mechanism in Langmuir monolayers of dihexadecyl phosphoric acid

The surface activity of the poly–[block (ethylene oxide)]–poly [block (propylene oxide)]–poly [block (ethylene oxide)] copolymers (EO)_x–(PO)_y–(EO)_x adsorbed together with dihexadecyl phosphoric acid (DHP), a synthetic phospholipid, is analyzed from their surface pressure and surface potential isotherms. The block copolymers of (EO)_x–(PO)_y–(EO)_x with variable molecular weight (1100–14 000) were dissolved in the subphase for DHP monolayers. The concentration of the copolymers within the aqueous subphase were selected to render an initial surface tension of 60 mN/m. The simultaneous adsorption of the copolymer and DHP is attested by the observation of a liquid expanded state at large areas, absent for pure DHP monolayers. Above some critical surface pressure all copolymers cited above are expelled from the interface. The surface potential isotherms, which give information on the component of the molecular dipole moment normal to the plane of the monolayer, are interpreted in terms of changes in the copolymer conformation as well as in terms of the copolymer desorption from the air–liquid interface. For an equal hydrophobic/hydrophilic ratio, the size of the chains or molecular weight is decisive in the mechanism of the copolymer expulsion from the air–liquid interface.     

Structural characteristics of dipalmitoylphosphatidylcholine and hydrolysates from sunflower protein isolate mixed monolayers spread at the air-water interface

In this work, surface film balance and Brewster angle microscopy techniques have been used to analyze the structural characteristics (structure, topography, reflectivity, thickness, miscibility, and interactions) of hydrolysates from sunflower protein isolate (SPI) and dipalmitoylphosphatidylcholine (DPPC) mixed monolayers spread on the air-water interface. The degree of hydrolysis (DH) of SPI, low (5.62%), medium (23.5%), and high (46.3%), and the protein/DPPC mass fraction were analyzed as variables. The structural characteristics of the mixed monolayers deduced from the surface pressure (pi)-area (A) isotherms depend on the interfacial composition and degree of hydrolysis. At surface pressures lower than the equilibrium surface pressure of SPI hydrolysate (pi(e)(SPI hydrolysate)), both DPPC and protein are present in the mixed monolayer. At higher surface pressures (at pi > pi(e)(SPI hydrolysate)), collapsed protein residues may be displaced from the interface by DPPC molecules. The differences observed between pure SPI hydrolysates and DPPC in reflectivity (I) and monolayer thickness during monolayer compression have been used to analyze the topographical characteristics of SPI hydrolysates and DPPC mixed monolayers at the air-water interface. The topography, reflectivity, and thickness of mixed monolayers confirm at microscopic and nanoscopic levels the structural characteristics deduced from the pi-A isotherms.     

Influence of a fluorescent probe on the nanostructure of phospholipid membranes: dipalmitoylphosphatidylcholine interfacial monolayers

Monolayers of dipalmitoylphosphatidylcholine (DPPC), both in the absence and in the presence of 1% (mol/mol) of a fluorescent phospholipid probe, have been spread at the air-liquid interface of a surface balance, compressed up to pressures in the liquid-expanded/liquid-condensed plateau of the isotherm, transferred onto mica supports, and analyzed by scanning force microscopy (SFM). Supported DPPC films showed micrometer-sized condensed domains with morphology and size that were entirely analogous to those observed in situ at the air-liquid interface by epifluorescence microscopy. The analysis by SFM, however, allowed the study and comparison of monolayers in the absence and in the presence of the fluorescent marker. This analysis revealed that the presence of dye reduced by 10-20% the total amount of the liquid-condensed phase in the DPPC films. The presence of the dye also decreased the mechanical stability of the film and increased the time required for the monolayer to equilibrate. The resolution of SFM permitted the determination that the structures of both the liquid-expanded and the liquid-condensed regions of DPPC films were heterogeneous at the nanometer scale. Liquid-condensed DPPC microdomains contained nanoholes covering 4-8% of their area whereas 60-80% of the surface detected as liquid-expanded by fluorescence microscopy consisted of a condensed-like framework of nanodomains. The total area, the shape of the nanodomains, and their interconnectivity were affected by the presence of the probe, suggesting that care must be taken when studying the structure, especially at the nanometer scale, and properties of model lipid films in the presence of extrinsic probes.     

Dynamic elasticity of triblock copolymer of poly(ethylene oxide) and poly(propylene oxide) on a water surface

Dilatational viscoelasticity of adsorbed and spread films of the poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer at the air-water interface is studied by the capillary waves and oscillating barrier techniques. At the surface pressure below 10 mN/m, dynamic surface properties of these films coincide with those of poly(ethylene oxide). At higher surface pressures, the results obtained indicate the desorption of poly(propylene oxide) segments from the monolayer and their interaction with poly(ethylene oxide) segments in an aqueous phase. At a surface pressure close to 19 mN/m, the behavior of adsorbed and spread poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) films becomes different. The real part of dynamic surface elasticity of spread films tends toward its maximum value (20 mN/m) and, upon further compression, films begin to dissolve. At the same time, the surface elasticity of adsorbed films decreases nearly twofold upon the achievement of the maximum value that testifies the formation of looser structure of the surface layer.     

Infrared reflection absorption spectroscopy coupled with Brewster angle microscopy for studying interactions of amphiphilic triblock copolymers with phospholipid monolayers

Novel water-soluble amphiphilic triblock copolymers poly(glycerol monomethacrylate)-b-poly(propylene oxide)-b-poly(glycerol monomethacrylate) (PGMA-b-PPO-b-PGMA) were synthesized because of their expected enhanced ability to interact with biological membranes compared to the well-known poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (PEO-b-PPO-b-PEO) block copolymers. Their bulkier hydrophilic PGMA blocks might induce a disturbance in the packing of liquid-crystalline lipid bilayers in addition to the effect caused by the hydrophobic PPO block alone. To gain a better insight into the polymer-membrane interactions at the molecular level, the adsorption kinetics and concomitant interactions of (PGMA14)(2-)PPO(34) with model membranes of dipalmitoylphosphatidylcholine (DPPC) and dimyristoylphosphatidylcholine (DMPC) were monitored using infrared reflection absorption spectroscopy (IRRAS) coupled with Brewster angle microscopy (BAM) and surface pressure (pi) measurements. The maximum penetration surface pressure of ca. 39 mN/m suggests that (PGMA14)(2-)PPO(34) is able to insert into lipid monolayers even above the so-called monolayer-bilayer equivalent pressure of 30-35 mN/m. Copolymer adsorption to a liquid-expanded DPPC-d62 monolayer proceeds in a two-step mechanism: (i) initially only the more hydrophobic PPO middle block penetrates the lipid monolayer; (ii) following the liquid-expanded-liquid-condensed (LE-LC) phase transition, the bulky PGMA hydrophilic blocks are dragged into the headgroup region as the PPO block inserts further into the fatty acid region. The adsorption kinetics is considerably faster for DMPC-d54 monolayers due to their higher fluidity. Copolymer adsorption to an LC-DPPC-d62 monolayer leads to a change in the monolayer packing by forcing the lipid alkyl chains into a more vertical orientation, their tilt angle with respect to the surface normal being reduced from initially 30 degrees +/- 3 degrees to 18 degrees +/- 3 degrees. BAM images rule out macroscopic phase separation and show that coalescence of DPPC-d62 LC domains takes place at relatively low surface pressures of pi > or = 23 mN/m, suggesting that (PGMA14)(2-)PPO (34) partitions into both LE as well as LC domains.     

Two-dimensional self-assembly of linear poly(ethylene oxide)-b-poly(epsilon-caprolactone) copolymers at the air-water interface

The interfacial properties of amphiphilic linear diblock copolymers based on poly(ethylene oxide) and poly(epsilon-caprolactone) (PEO-b-PCL) were studied at the air-water (A/W) interface by surface pressure measurements (isotherms and hysteresis experiments). The resulting Langmuir monolayers were transferred onto mica substrates and the Langmuir-Blodgett (LB) film morphologies were investigated by atomic force microscopy (AFM). All block copolymers had the same PEO segment (Mn = 2670 g/mol) and different PCL chain lengths (Mn = 1270; 2110; 3110 and 4010 g/mol). Isothermal characterization of the block copolymer samples indicated the presence of three distinct phase transitions around 6.5, 10.5, and 13.5 mN/m. The phase transitions at 6.5 and 13.5 mN/m correspond to the dissolution of the PEO segments in the water subphase and crystallization of the PCL blocks above the interface similarly as for the corresponding homopolymers, respectively. The phase transition at 10.5 mN/m was not observed for the homopolymers alone or for their blends and arises from a brush formation of the PEO segments anchored underneath the adsorbed hydrophobic PCL segments. AFM analysis confirmed the presence of PCL crystals in the LB films with unusual hairlike/needlelike architectures significantly different from those obtained for PCL homopolymers.     

Fabrication of block copolymer monolayers by adsorption from supercritical fluids: a versatile concept for modification and functionalization of polymer surfaces

We describe a generic method for polymer surface modification and functionalization that is applicable for substrates of arbitrary shape. The method involves the deposition of monolayer and submonolayer films of photoactive block copolymers from supercritical fluids. Poly(styrene-b-tert-butyl acrylate), poly(S-b-tBA), block copolymer monolayers form spontaneously on polystyrene substrates by adsorption from scCO2 when hexane is used as a cosolvent. Atomic force microscopy indicates the films are flat and without pores after modification. Ethylene glycol contact angles increase linearly with deposition pressure until a constant value, equal to that of pure P tBA, is attained at pressures of 18 MPa or greater at 40 degrees C. This trend mimics the change in block copolymer solubility with pressure and indicates that the block copolymer self-assembles and orders at the surface, presenting a P tBA layer at the air interface with the PS block orienting toward the PS substrate. The P tBA layer thickness, determined by angle dependent X-ray photoelectron spectroscopy, reaches a saturated monolayer value of ca. 2 nm for pressures of 18 MPa and higher, consistent with the thickness expected for unperturbed PtBA chains comprising a wet brush. This concept for polymer surface modification initially produces a hydrophobic surface due to surface adsorption of the low surface tension PtBA block, but can also be used to prepare hydrophilic, functional surfaces, either modified or patterned with carboxylic acid groups, by photolytic or acid catalyzed deprotection/hydrolysis of the tert-butyl ester groups.     

Poly(ethylene oxide)-poly(styrene oxide)-poly(ethylene oxide) copolymers: Micellization, drug solubilization, and gelling features

Two new poly(ethylene oxide)-poly(styrene oxide) triblock copolymers (PEO-PSO-PEO) with optimized block lengths selected on the basis of previous studies were synthesized with the aim of achieving a maximal solubilization ability and a suitable sustained release, while keeping very low material expense and excellent aqueous copolymer solubility. The self-assembling and gelling properties of these copolymers were characterized by means of light scattering, fluorescence spectroscopy, transmission electron microscopy, and rheometry. Both copolymers formed spherical micelles (12-14 nm) at very low concentrations. At larger concentration (>25 wt%), copolymer solutions showed a rich phase behavior, with the appearance of two types of rheologically active (more viscous) fluids and of physical gels depending on solution temperature and concentration. The copolymer behaved notably different despite their relatively similar block lengths. The ability of the polymeric micellar solutions to solubilize the antifungal drug griseofulvin was evaluated and compared to that reported for other structurally-related block copolymers. Drug solubilization values up to 55 mg g⁻¹ were achieved, which are greater than those obtained by previously analyzed poly(ethylene oxide)-poly(styrene oxide), poly(ethylene oxide)-poly(butylene oxide), and poly(ethylene oxide)-poly(propylene oxide) block copolymers. The results indicate that the selected SO/EO ratio and copolymer block lengths were optimal for simultaneously achieving low critical micelle concentrations (cmc) values and large drug encapsulation ability. The amount of drug released from the polymeric micelles was larger at pH 7.4 than at acidic conditions, although still sustained over 1 day.     

Temperature dependence of poloxamer insertion into and squeeze-out from lipid monolayers

F68, a triblock copolymer of the form poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide), is found to effectively seal damaged cell membranes. To better understand the molecular interaction between F68 and cells, we have modeled the outer leaflet of a cell membrane with a dipalmitoylphosphatidylcholine (DPPC) monolayer spread at the air-water interface and introduced poloxamer into the subphase. Subsequent interactions of the polymer with the monolayer either upon expansion or compression were monitored using concurrent Langmuir isotherm and fluorescence microscopy measurements. To alter the activity of the poloxamer, a range of subphase temperatures from 5 to 37 degrees C was used. Lower temperatures increase the solubility of the poloxamer in the subphase and therefore lessen the amount of material at the interface, resulting in a lower equilibrium spreading pressure. Additionally, changes in temperature affect the phase behavior of DPPC. Below the triple point, the monolayer is condensed at pertinent polymer insertion pressures; for temperatures immediately above the triple point, the monolayer is a heterogeneous mix of liquid expanded and condensed phase; for the highest temperature measured, the DPPC monolayer remains completely fluid. At all temperatures, F68 inserts into DPPC monolayers at its equilibrium spreading pressure. Upon compression of the monolayer, polymers are squeezed-out at surface pressures notably higher than those for insertion, with higher temperatures leading to a higher squeeze-out pressure. An increase in temperature decreases the solvent quality of water for the poloxamer, lowering solubility of the polymer in the subphase and thus increasing its propensity to be maintained within the monolayer to higher pressures.     

Study of adsorption and penetration of E2(279-298) peptide into Langmuir phospholipid monolayers

The peptide corresponding to the sequence (279-298) of the Hepatitis G virus (HGV/GBV-C) E2 protein was synthesized, and surface activity measurements, pi-A compression isotherms, and penetration of E2(279-298) into phospholipid monolayers spread at the air-water interface were carried out on water and phosphate buffer subphases. The results obtained indicated that the pure E2(279-298) Langmuir monolayer exhibited a looser packing on saline-buffered than on pure water subphase and suggest that the increase in subphase ionic strength stabilizes the peptide monolayer. To better understand the topography of the monolayer, Brewster angle microscopy (BAM) images of pure peptide monolayers were obtained. Penetration of the peptide into the pure lipid monolayers of dipalmitoylphosphatidylcholine (DPPC) and dimyristoylphosphatidylcholine (DMPC) and into mixtures of dimyristoylphosphatidylcholine/dimyristoylphosphatidylglycerol (DMPC/DMPG) at various initial surface pressures was investigated to determine the ability of these lipid monolayers to host the peptide. The higher penetration of peptide into phospholipids is attained when the monolayers are in the liquid expanded state, and the greater interaction is observed with DMPC. Furthermore, the penetration of the peptide dissolved in the subphase into these various lipid monolayers was investigated to understand the interactions between the peptide and the lipid at the air-water interface. The results obtained showed that the lipid acyl chain length is an important parameter to be taken into consideration in the study of peptide-lipid interactions.     

Pressure- and temperature-induced association of arborescent polystyrene-graft-poly(ethylene oxide) copolymers at the air-water interface

The influence of surface pressure and subphase temperature on the association of arborescent polystyrene- graft-poly(ethylene oxide) (PS- g-PEO) copolymers at the air-water interface was investigated using the Langmuir balance and atomic force microscopy (AFM) techniques. These dendritic molecules form stable condensed monolayers with surface compressional moduli >250 mN/m. The variation in film thickness observed as a function of surface pressure suggests that at low surface pressures (gaslike phase) the PEO chains remain adsorbed at the air-water interface. At higher surface pressures (condensed phase), the PEO chains partially desorb into the subphase and adopt a more brushlike conformation. Large islandlike clusters with a broad size distribution were observed for samples with PEO contents of up to 15% by weight. In contrast, copolymers with PEO contents of 22-43% displayed enhanced side-by-side association into ribbonlike superstructures upon compression. The same effect was observed even in the absence of compression when the subphase temperature was increased from 12 to 27 degrees C. The temperature-induced association was attributed to increased van der Waals attractive forces between the PS cores relative to the steric repulsive forces between PEO chains in the coronas because the solvent quality for the PEO segments decreased at higher temperatures. The restricted number of superstructures observed for arborescent copolymers as compared with linear- and star-branched PS-PEO block copolymers is attributed to the enhanced structural rigidity of the molecules due to branching.     

Monolayer properties of mixtures of poly(n-stearyl methacrylate), poly(n-lauryl methacrylate), and their corresponding copolymers

The monolayer properties of poly(n-stearyl methacrylate), poly(n-lauryl methacrylate), and their mixtures at various ratios of the two polymers have been studied from the measurements of their surface pressure–area isotherms at air–water interface. The monolayer properties of their mixtures have been compared with those of their corresponding copolymers. The results show that the isotherms of the mixed monolayers have two break points at higher pressures than that of poly(n-lauryl methacrylate). This suggests that the mixtures may form more stable films that consist of separate phases of the two homopolymers, although each phase may contain a small amount of the other. The isotherms of the copolymer monolayers indicate a phase transition from liquid condensed to solid film between 50 segment mole % and 70% poly(n-stearyl methacrylate). The monclayer of these copolymers has properties that differ from those of the corresponding mixtures of two pure homopolymers and is more compatible than the mixtures of pure homopolymers.     

On the interaction of dipalmitoyl phosphatidylcholine with normal long-chain alcohols in a mixed monolayer: a thermodynamic study

This study investigated the mixed monolayer behavior of dipalmitoyl phosphatidylcholine (DPPC) with normal long-chain alcohols at the air/water interface. Surface pressure–area isotherms of mixed DPPC/C₁₈OH and DPPC/C₂₀OH monolayers at 37°C were obtained and compared with previous results for the mixed DPPC/C₁₆OH system. The negative deviations from additivity of the areas and the variation of the collapse pressure with composition imply that DPPC and long-chain alcohols were miscible and formed non-ideal monolayers at the interface. At lower surface pressures, it seems that the attractive intermolecular force was dominant in molecular packing in the mixed monolayers. At higher surface pressures, the data suggest that the molecular packing in mixed DPPC/C₁₆OH monolayers may be favored by the packing efficiency or geometric accommodation. Furthermore, negative values of excess free energy of mixing were obtained and became significant as the hydrocarbon chain length of alcohols increased, which indicates there were attractive interactions between DPPC and long-chain alcohols. In each free energy of mixing–composition curve, there was only one minimum and thus a phase separation did not exist for mixed DPPC/long-chain alcohol monolayers.     

Structural and topographical characteristics of dipalmitoyl phosphatidic acid in Langmuir monolayers

Dipalmitoyl phosphatidic acid (DPPA) monolayers at the air-water interface were studied from surface pressure (Pi)-area (A) isotherms and at the microscopic level with Brewster angle microscopy (BAM) under different conditions of temperature, pH, and ionic strength. BAM images were recorded simultaneously with Pi-A isotherms during the monolayer compression-expansion cycles. DPPA monolayers show a structural polymorphism from the liquid-expanded (LE)-liquid-condensed (LC) transition region at lower surface pressures toward liquid-condensed and solid (S) structures at higher surface pressures. An increase in temperature, pH, or ionic strength provokes an expansion in the monolayer structure. The results obtained from the Pi-A measurements are confirmed by the monolayer topography and relative reflectivity. The measurements of relative reflectivity upon monolayer compression showed an increase in relative monolayer thickness of 1.25 and 3.3 times throughout the full monolayer compression from the liquid-expanded to the liquid-condensed and solid states, respectively.     

Adsorption of poly(ethylene oxide)-b-poly(epsilon-caprolactone) copolymers at the silica-water interface

The adsorption of amphiphilic poly(ethylene oxide)-b-poly(epsilon-caprolactone) and poly(ethylene oxide)-b-poly(gamma-methyl-epsilon-caprolactone) copolymers in aqueous solution on silica and glass surfaces has been investigated by flow microcalorimetry, small-angle neutron scattering (SANS), surface forces, and complementary techniques. The studied copolymers consist of a poly(ethylene oxide) (PEO) block of M(n) = 5000 and a hydrophobic polyester block of poly(epsilon-caprolactone) (PCL) or poly(gamma-methyl-epsilon-caprolactone) (PMCL) of M(n) in the 950-2200 range. Compared to homoPEO, the adsorption of the copolymers is significantly increased by the connection of PEO to an aliphatic polyester block. According to calorimetric experiments, the copolymers interact with the surface mainly through the hydrophilic block. At low surface coverage, the PEO block interacts with the surface such that both PEO and PCL chains are exposed to the aqueous solution. At high surface coverage, a dense copolymer layer is observed with the PEO blocks oriented toward the solution. The structure of the copolymer layer has been analyzed by neutron scattering using the contrast matching technique and by tapping mode atomic force microscopy. The experimental observations agree with the coadsorption of micelles and free copolymer chains at the interface.     

Surface Dynamic Elasticity of Amphiphilic Block Copolymer Monolayers on a Water Surface

The methods of longitudinal and transverse surface waves and of oscillating barrier were used to measure a surface dynamic elasticity of the monolayers of poly(ethylene oxide) and polystyrene block copolymers spread on water within the frequency range of 0.007–520 Hz. At low surface concentrations, the properties of monolayers are determined by the poly(ethylene oxide) block. Upon further monolayer compression, the transition to the regime of polymer brush occurs when the surface dynamic elasticity increases dramatically. Change in the molecular weight of poly(ethylene oxide) block does not lead to the qualitative change in the dependence of surface properties on the degree of monolayer compression. Surface viscosity in the regime of brush significantly differs from the results of calculations made by Buzzaet al. [26]. Possible reasons for this difference are discussed.