Nanostructure and transition of a strong polyelectrolyte brush at the air/water interface

The strong polyelectrolyte layer in the monolayer of ionic amphiphilic diblock copolymers at the air/water interface consists of carpet and brush layers when the brush density is satisfactorily high like that of the weak acid polymer. Also, a drastic structural change was induced by the addition of salt to the brush layer. In this study, the critical brush density for the transition between "carpet-only" and "carpet + brush" structures for the strongly ionic amphiphilic diblock copolymer, poly(hydrogenated isoprepene)-b-poly(styrene sulfonic acid) sodium salt, monolayer was measured by an in situ X-ray reflectivity technique. The critical brush density was found to be about 0.12 nm-2, which is lower than that observed for a weak acid polymer and, unlike the weak acid polymer, is independent of the hydrophilic chain length. This difference might be attributed to the strong ionic nature of the brush chain. In addition, the reversibility of the transition was confirmed. The effect of salt addition to the nanostructure of the carpet layer was examined in detail. No structural change was found, indicating that most of the ionic groups in the carpet layer do not show an ionic nature because of counterion condensation.     

Carpetlike dense‐layer formation in a polyelectrolyte brush at the air/water interface

A carpetlike dense‐layer formation between a hydrophobic layer and a polyelectrolyte brush layer has been found in the monolayers of an ionic amphiphilic diblock copolymer, poly(1,1‐diethylsilacyclobutane)_m‐block‐poly(methacrylic acid)_n, on a water surface by an X‐ray reflectivity technique. By detailed analysis, we have found that the hydrophilic layer under the water is not a simple layer but is divided into two layers, that is, a carpetlike dense methacrylic acid (MAA) layer near the hydrophobic layer and a polyelectrolyte brush layer. We have also confirmed that a well‐established polyelectrolyte brush is formed only for the m:n = 43:81 polymer monolayer: For m:n = 40:10 and m:n = 45:60 polymer monolayers, only a dense MAA layer is formed. This dense‐layer formation should be the origin of the interesting hydrophobic‐layer thickness variation previously reported; The hydrophobic‐layer thickness takes a minimum as a function of the hydrophilic chain length at any surface pressure studied. An overview of the data for three samples with different chain lengths (m:n = 40:10, 45:60, or 43:81) has shown that the thickness of this dense layer is 10–20 Å and is independent of the surface pressure and polymerization degree of poly(methacrylic acid) (PMAA) in the range studied. This dense‐layer formation is explained by the reasonable speculation that contact with PMAA is thermodynamically more stable than direct contact with water for the diethylsilacyclobutane (Et₂SB) layer on water. In this sense, the dense layer acts like a carpet for the hydrophobic Et₂SB layer, and a 10–20‐Å thickness could be a critical value for the carpet. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1921–1928, 2003     

Hierarchical nanoparticle/block copolymer surface features via synergistic self-assembly at the air-water interface

This work demonstrates the first example of the controlled organization of semiconducting nanoparticles (NPs) using amphiphilic block copolymer self-assembly at the air-water interface. Preferential interactions between polystyrene-functionalized NPs and the polystyrene block of an amphiphilic polystyrene-b-poly(ethylene oxide) block copolymer result in synergistic self-assembly at the air-water interface, forming a range of highly stable one-dimensional NP/polymer surface features, including branched nanowires, nanocables up to 100 microm in length, and nanowires with nanoring connectors. This strategy offers new routes to hierarchical hybrid assemblies with potential photonics applications because the nanoscale organization of NPs is coupled to features with dimensions that are commensurate with optical wavelengths.     

Structural analysis of PEO-PBO copolymer monolayers at the air-water interface

X-ray reflectivity (XR) and grazing incidence X-ray diffraction (GIXD) have been used to examine an oxyethylene-b-oxybutylene (E(23)B(8)) copolymer film at the air-water interface. The XR data were fitted using both a one- and a two-layer model that outputted the film thickness, roughness, and electron density. The best fit to the experimental data was obtained using a two-layer model (representing the oxyethylene and oxybutylene blocks, respectively), which showed a rapid thickening of the copolymer film at pressures above 7 mN/m. The large roughness values found indicate a significant degree of intermixing between the blocks and back up the GIXD data, which showed no long range lateral ordering within the layer. It was found from the electron density model results that there is a large film densification at 7 mN/m, possibly suggesting conformational changes within the film, even though no such change occurs on the pressure-area isotherm at the same surface pressure.     

Monolayer formation of PBLG-PEO block copolymers at the air-water interface

Physicochemical properties of PBLG (poly(gamma-benzyl-l-glutamate))-PEO (poly(ethylene oxide)) diblock copolymers composed of PBLG as the hydrophobic rod component and PEO as the hydrophilic component were investigated at the air-water interface. Surface pressure-area isotherms obtained by the Wilhelmy plate method provide several variables such as molecular size, compressibility of PEO, and the free energy change of the PBLG-PEO block copolymer. GE-1 (M(w) of PBLG:PEO=103,700:12,000), with a relatively longer rod, has negative temperature effects and GE-3 (M(w) of PBLG:PEO=8400:12,000), with a relatively shorter rod, shows a positive temperature effect because of the large entropy loss. These competitions were based on the block size of PBLG and PEO and were affected by various microstructures of the PBLG-PEO diblock copolymer. Monolayer aggregations transferred onto mica from the air-water interface were analyzed with AFM. AFM images of GE-1 monolayers show cylindrical micelles, but the self-assembled structure has many large domains. The monolayer of GE-2 (M(w) of PBLG:PEO=39,800:12,000), which has a medium size rod, forms a spherical structure at the air-water interface. Monolayers of GE-3, with a short rod length, form bilayer structures. These results demonstrate that the microstructures of PBLG-PEO diblock copolymers are related to free energy changes between rod and coil blocks.     

Thermoresponsive reversible behavior of multistimuli pluronic-based pentablock copolymer at the air-water interface

Surface behavior of the pH- and thermoresponsive amphiphilic ABCBA pentablock copolymer has been studied with respect to the environmental conditions. We demonstrate that the pentablock copolymer poly((diethylaminoethyl methacrylate)-b-(ethylene oxide)-b-(propylene oxide)-b-(ethylene oxide)-b-(diethylaminoethyl methacrylate)) possesses reversible temperature changes at the air-water interface in a narrow pH range of the water subphase. Significant diversity in the surface morphology of pentablock copolymer monolayers at different pH and temperatures observed were related to the corresponding reorganization of central and terminal blocks. Remarkable reversible variations of the surface pressure observed for the Langmuir monolayers at pH 7.4 in the course of heating and cooling between 27 and 50 degrees C is associated with conformational transformations of terminal blocks crossing the phase line in the vicinity of the lower critical solution temperature point. The observed thermoresponsive surface behavior can be exploited for modeling of the corresponding behavior of pentablock copolymers adsorbed onto various biointerfaces for intracellular delivery for deeper understanding of stimuli-responsive transformations relevant to controlled drug and biomolecules release and retention.     

Kinetics for the collapse of trilayer liquid-crystalline disks from a monolayer at an air-water interface

Unlike surfactants considered in previous studies, when phosphatidylcholine (PC) monolayers collapse at constant surface tension to form a 3D bulk phase, surface area decreases at rates that slow. The different kinetics could result from collapse by a distinct mechanism. Rather than the transfer of molecules all along the interface between the monolayer and bulk phase, PC films can collapse by the folding and subsequent sliding of a bilayer over the monolayer. By this mechanism, molecules can transfer to collapsed trilayers through a locus of constant size. In this article, we use the theory of nucleation and growth to show analytically that during collapse, the area can decrease at rates that decelerate when each individual structure grows through a region of fixed dimensions. We also show that binary films of 30% dihydrocholesterol (dchol) and dipalmitoyl phosphatidylcholine (DPPC), which have previously been shown to form a homogeneous monolayer from which trilayer disks grow through a point, collapse with rates of area decay that slow, in agreement with our analytical expressions.     

Phase transition in an adsorption layer of a soluble surfactant at the air-water interface

In this paper we provide experimental evidence for a phase transition between a liquid- and gas-like phase occurring in an adsorption layer of a soluble surfactant at the air-water interface. The equilibrium surface tension sigma(e) versus bulk concentration sigma(e) (c) isotherm of surface chemically pure sodium 2-[4-(4-trifluoromethyl-phenylazo) phenoxy]-ethane sulfonate was measured at a temperature of 295 K up to the solubility limit of the amphiphile. The sigma(e) (c) isotherm could be fitted by Frumkin's equation of state. The lateral interaction energy is just above the limit for which Frumkin's model predicts a phase transition. The corresponding surface pressure pi versus surface area A isotherm possesses striking similarities to first-order phase transitions in the Langmuir monolayer. The fact that the difference in the two-dimensional density is only a factor of 2 indicates that the system is very close to the critical point. The surface phases were further characterized by surface second harmonic generation. The major structural difference between the two surface phases is the amphiphile's molecular orientation. A mean orientation of the amphiphile of about 80 degrees was found in the gas analogous phase, whereas a molecular tilt of 38 degrees has been identified in the liquid-like phase.     

Formation of silver nanoparticles at the air-water interface mediated by a monolayer of functionalized hyperbranched molecules

Nanofibrillar micellar structures formed by the amphiphilic hyperbranched molecules within a Langmuir monolayer were utilized as matter for silver nanoparticle formation from the ion-containing water subphase. We observed that silver nanoparticles were formed within the multifunctional amphiphilic hyperbranched molecules. The diameter of nanoparticles varied from 2-4 nm and was controlled by the core dimensions and the interfibrillar free surface area. Furthermore, upon addition of potassium nitrate to the subphase, the Langmuir monolayer templated the nanoparticles' formation along the nanofibrillar structures. The suggested mechanism of nanoparticle formation involves the oxidation of primary amino groups by silver catalysis facilitated by "caging" of silver ions within surface areas dominated by multibranched cores. This system provides an example of a one-step process in which hyperbranched molecules with outer alkyl tails and compressed amine-hydroxyl cores mediated the formation of stable nanoparticles placed along/among/beneath the nanofibrillar micelles.     

Ellipsometric characterization of ethylene oxide-butylene oxide diblock copolymer adsorption at the air-water interface

Ellipsometry was used to determine the adsorbed layer thickness (d) and the surface excess (adsorbed amount, Gamma) of a nonionic diblock copolymer, E(106)B(16), of poly(ethylene oxide) (E) and poly(butylene oxide) (B) at the air-water interface. The results were obtained (i) by the conventional ellipsometric evaluation procedure using the change of both ellipsometric angles Psi and Delta and (ii) by using the change of Delta only and assuming values of the layer thickness. It was demonstrated that the calculated surface excesses from the different methods were in close agreement, independent of the evaluation procedure, with a plateau adsorption of about 2.5 mg/m(2) (400 A(2)/molecule). Furthermore, the amount of E(106)B(16) adsorbed at the air-water interface was found to be almost identical to that adsorbed from aqueous solution onto a hydrophobic solid surface. In addition, the possibility to use combined measurements with H(2)O or D(2)O as substrates to calculate values of d and Gamma was investigated and discussed. We also briefly discuss within which limits the Gibbs equation can be used to determine the surface excess of polydisperse block copolymers.     

Surface rheology of hydrophobically modified PEG polymers associating with a phospholipid monolayer at the air-water interface

Surface rheology of irreversibly bound hydrophobically modified poly(ethylene glycol) (PEG) polymers (HMPEG) on a dipalmitoylphosphatidylcholine (DPPC) monolayer is investigated to determine attributes that may contribute to immune recognition. Previously, three comb-graft polymers (HMPEG136-DP3, HMPEG273-DP2.5, and HMPEG273-DP5) adsorbed on liposomes were examined for their strength of adsorption and protection from complement binding. The data supported an optimal ratio between the hydrophilicity of the PEG polymer and the number of hydrophobic anchors. The HMPEG polymers have different polymer brush thicknesses (4.2-5.9 nm) and levels of cooperativity (2.5-5 hydrophobes). The results indicate that an increased viscous force (above 0.25 mN s/m) at the surface may enable the polymers to shield liposomes from protein interactions. Similar rheological behavior is shown for all polymer architectures at low polymer surface coverage (0.5 mg/m2, in the mushroom regime), whereas at high surface coverage (>0.5 mg/m2, in the brush regime), we observe a structural dependence of the surface viscous forces at 40 mN/m. This threshold correlates with a 92% decrease in complement protein binding for liposomes coated with 1 mg/m2 HMPEG273-DP5. This may suggest that surface viscous forces play a role in reducing complement protein binding.     

Sliding friction at a rubber/brush interface

We study the friction of a poly(dimethylsiloxane) (PDMS) rubber network sliding, at low velocity, on a substrate on which PDMS chains are end-tethered. We thus clearly evidence the contribution to friction of the pullout mechanism of chain ends that penetrate into the network. This interfacial dissipative process is systematically investigated by probing the velocity dependence of the friction stress and its variations with the grafting density and molecular weight of the tethered chains. This allows us to confirm semiquantitatively the picture of arm retraction relaxation of the grafted chains proposed in models of slippage at a network/brush interface.     

Strands, networks, and continents from polystyrene dewetting at the air-water interface: implications for amphiphilic block copolymer self-assembly

We demonstrate that nanoscale aggregates similar to those formed via amphiphilic block copolymer self-assembly at the air-water interface, including strands, networks, and continents, can be generated by the simple spreading of PS homopolymer solutions on water. Two different PS homopolymers of different molecular weight (PS-405k, M(n) = 405?000 g mol(-1) and PS-33k, M(n) = 33?000 g mol(-1)) are spread at the air-water interface at various spreading concentrations ranging from 0.25 to 3.0 mg/mL. Aggregate formation is driven by PS dewetting from water as the spreading solvent evaporates. We propose that a high spreading concentration or a high molecular weight lead to chain entanglements that restrict macromolecular mobility in the solution, enabling the kinetic trapping of nanostructures associated with early and intermediate stages of PS dewetting. Comparison of PS-405k with a mainly hydrophobic PS-b-PEO block copolymer of similar molecular weight (PSEO-392k, M(n) = 392?000 g mol(-1), 2.0 wt % PEO) allows the effect of a relatively short surface active block on aggregate formation to be investigated. We show that whereas the PEO block is not a required component for the formation of strands and other nonglobular aggregates, it does increase the number of these aggregates at a given spreading concentration and decreases the minimum spreading concentration at which these aggregates are observed, along with decreasing the dimensions and polydispersity of specific surface features. The results provide supporting evidence for the role of PS dewetting in the generation of multiple PS-b-PEO aggregate morphologies at the air-water interface, as originally described in earlier paper from our group.     

Microphase separation in mixed monolayers of DPPG with a double hydrophilic block copolymer at the air-water interface: a BAM, LSCFM, and AFM study

Phase separation and interactions in mixed monolayers of dipalmitoylphosphatidylglycerol (DPPG) with the rhodamine B end-labeled double-hydrophilic block copolymer (DHBC), poly(N,N-dimethylacrylamide)-block-poly(N,N-diethylacrylamide) (RhB-PDMA(207)-b-PDEA(177)), was studied at the air-water interface. Surface pressure versus area isotherms indicate that both components behave almost independently. Brewster angle microscopy (BAM) images show a random distribution of liquid condensed (LC) domains of DPPG in an apparent homogeneous matrix of DHBC, excluding the macroscopic phase separation. The laser scanning confocal fluorescence microscopy (LSCFM) of the rhodamine dye at the end of the PDMA chain showed how the DHBC is distributed in Langmuir-Blodgett (LB) mixed monolayers. The high spatial resolution of atomic force microscopy (AFM) combined with the LCSFM images indicates that DHBC incorporates in the expanded phase of DPPG to form mixed domains, being excluded from the condensed regions. Upon compression, nanosized LC domains of DPPG nucleate inside the mixed domains corralled in the nanopatterning of pure DHBC. The negatively charged polar group of DPPG inhibits rhodamine aggregation, while the long polymer chains promote the formation of corralled nanodomains of DPPG in two dimensions.     

Mechanical control of enantioselectivity of amino acid recognition by cholesterol-armed cyclen monolayer at the air-water interface

Monolayers of the cholesterol-armed cyclen Na+ complex at the air-water interface display a remarkable, surface pressure dependent enantioselectivity of amino acid recognition. Upon compression of the monolayer, the binding constants of amino acids increase accompanying an inversion of chiral selectivity from the d- to l-form in the case of valine.     

Kinetics and layer organization during the polymerization of coniferyl alcohol at the air-water interface

The initial stage of the polymerization of coniferyl alcohol catalyzed by a peroxydase was studied at the air-water interface. The properties of the monolayers were investigated at constant area and at constant surface pressure by surface pressure, surface potential and ellipticity measurements. On the basis of the results obtained at constant surface area, it is proposed that the formation of a 2D layer occurs up to the inflection point of the surface pressure-area isotherm, and that for larger surface pressures a 3D structure is formed during the polymerization. If the barostat is set at the inflection point (the surface pressure is constant while the surface area increases), the 2D organization of the monolayer is retained. A kinetic model describing the adsorption of the reaction products in a 2D layer is proposed. The kinetic constants were determined from the surface potential, ellipsometry, surface pressure and surface area data.     

Brewster angle microscopic study of mixed lipid-protein monolayer at the air-water interface and its application in biosensing

This study investigated lipid-protein LB film formation with Brewster angle microscopy. Our experimental results show that hemoglobin (Hb) molecules can enter the lipid layer and remain for an extended time. We investigated the KCl effect on the LB monolayer of lipid-protein. The lipid-Hb monolayer was transferred from the air-water interface to a QCM gold electrode. UV-vis spectra showed that Hb retained its natural structure in the lipid layer. Cyclic voltammetric (CV) and amperometric systems were applied in this study in order to confirm the remaining bioactivity and sensitivity of Hb to hydrogen peroxide (H(2)O(2)). Lipid-Hb-modified electrodes showed well-defined redox peaks, indicating that the direct electron transfer between Hb and the electrode was enhanced by Hb incorporated in lipid layer. Based on this phenomenon, a novel biosensor for H(2)O(2) was designed. Experimental conditions influencing the biosensor performance such as pH, and potential were optimized and assessed. The levels of the R.S.D.'s (<5%) for the entire analyses reflected the highly reproducible sensor performance. Using optimized conditions the linear range for the detection of H(2)O(2) was observed from 1 x 10(-6) to 1.00 x 10(-4) molL(-1) with a detection limit of 4.00 x 10(-7) molL(-1) (based on the S/N=3).     

Dilational viscoelasticity of PEO-PPO-PEO triblock copolymer films at the air-water interface in the range of high surface pressures

The dynamic dilational elasticity of adsorbed and spread films of PEO-PPO-PEO triblock copolymers at the air-water interface was measured as a function of surface pressure, surface age, and frequency. At low surface pressures (<10 mN/m), the surface viscoelasticity is identical to that of PEO homopolymer films. The results at higher surface pressures can be explained by the desorption of PPO segments from the interface and then mixing with PEO segments in water. Unlike some recent results, the spread and adsorbed films are not identical. Spread films exhibit a maximum real part of the dynamic surface elasticity of about 20 mN/m and probably begin to dissolve in water at surface pressures above 19 mN/m. However, the surface elasticity of the adsorbed films decreases beyond the maximum, indicating the formation of a loose surface structure.     

Epoxy oligomer and cyclen polymerization on the air-water interface. Receptor properties of a monolayer

Two-dimensional functional polymer systems have been obtained for the first time based on an epoxy oligomer and 1,4,7,10-tetraazacyclododecane (cyclen). The effect of UV radiation on the efficiency of polymerization in the system has been studied. The morphology of polymer materials formed on the liquid surface as a result of thermo- and UV-induced polymerization has been studied. It has been shown that a polymer Langmuir monolayer based on an epoxy oligomer-cyclen mixture can be used as a sensor for copper ions, and the conditions for the system regeneration have been determined. Changes in the pH of the subphase have been established as causing structural rearrangements in the polymer monolayer, which lead to changes in the optical properties of the latter.