Biodegradable poly(dl-lactide)/poly(ε-caprolactone) mixtures: Miscibility at the air/water interface

Mixtures of biodegradable polymers, poly(dl-lactide) and poly(ε-caprolactone) monolayers at the air/water interface have been studied. Surface pressure-area isotherms of poly(dl-lactide), poly(ε-caprolactone) and their mixtures were obtained by monolayer compression at constant temperature. The behavior of the mixed monolayers was analyzed according to the classical addition rule. Good agreement was observed between experimental and ideal behavior except for one composition where a negative deviation was observed. The polymer monolayer miscibility was corroborated by comparison between the surface pressure-area isotherms of the random copolymers (dl-lactide-co-ε-caprolactone) and their mixtures at the same compositions. Brewster angle microscopy (BAM) shows homogeneity in the monolayers in the whole range of compositions. These results also confirm the miscibility of the mixtures.     

Assembly of oriented zeolite monolayers and thin films on polymeric surfaces via hydrogen bonding

The b-oriented monolayers of microsized silicalite-1 crystals have been manually assembled on glass plate supported poly(ethylene oxide) (PEO), poly(vinyl alcohol) (PVA), chitosan, and poly(methyl methacrylate) (PMMA) thin films via hydrogen bonding with much enhanced binding strength and satisfactory degrees of coverage and close packing. The exerted pressure and rubbing time in the manual assembly do not affect the binding strength of the silicalite-1 monolayer on the glass plate supported polymeric film. This manual assembly has been further applied to fabricate zeolite monolayers on commercially available Plexiglas surfaces and b-oriented multilayered films of silicalite-1 crystals on glass plates. The assembly method established in this study provides a feasible way to produce zeolite monolayers on polymer-modified solid substrates and Plexiglas and to fabricate zeolite-polymer composite membranes by means of the layer-by-layer technique.     

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

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

Gluing Langmuir-Blodgett monolayers onto hydrocarbon surfaces

This paper describes a new approach for modifying hydrophobic surfaces that is based on the use of ionically cross-linked (i.e., "glued") Langmuir-Blodgett monolayers. Specifically, this work shows how monolayers of 5,11,17,23,29,35-hexa(trimethylammonium methyl)-37,38,39,40,41,42-hexakis-n-hexadecyloxy-calix[6]arene (1a), which have been ionically cross-linked with poly(4-styrene-sulfonate) (PSS, MW 30,000-50,000), can be deposited onto silylated silicon wafers with their polar headgroups extending outward into air. This work also demonstrates the feasibility of using glued monolayers of 1a as "anchors" for attaching alternating layers of poly(diallyldimethylammonium) [PDADMA] and PSS ions onto these same hydrocarbon surfaces.     

Poly(itaconates) monolayers behavior at the air/water interface. Study at different surface concentration

Polymer monolayers spread at the air/water interface were obtained for: poly(monooctyl itaconate) (PMOI), poly(monodecyl itaconate) (PMDI), poly(monododecyl itaconate) (PMDoI), poly(monobenzyl itaconate) (PMBzI), poly(methyldodecyl itaconate) (PMeDoI) and the alternating copolymer (monooctyl itaconate-alt-maleic anhydride) (MOI-alt-MA). By monolayer compression at constant temperature, the respective Langmuir isotherms for these polymers were obtained. For all polymers the zero-pressure limiting area per repeating unit (ru) Ao, and the collapse pressure π_c were determined. At low surface polymer concentrations, the monolayers characterization was carried out according to the surface pressure expressed as a function of the surface concentration. The behavior observed was described by the virial expansion development. At the semidilute region, the surface pressure variation was expressed in terms of the scaling laws as a power function of the surface concentration.     

Polymer monolayers with a photosensitive crown‐ether

The mixed monolayers of a photosensitive crown‐ether (CE) and poly(maleic acid hexadecyl monoamide‐alt‐propylene) (P12) have been prepared and studied. Fluorescence spectra of CE have a strong band at 530–535 nm in solution (monomer) or at 593–603 nm in transferred monolayers (aggregates). Due to the interaction with polymer the fluorescence maximum of CE is shifted to 530 nm in the mixed monolayers with P12.     

Choose sides: differential polymer adhesion

AFM-based single molecule desorption measurements were performed on surface end-grafted poly(acrylic acid) monolayers as a function of the pH of the aqueous buffer to study the adhesion properties of polymers that bridge two surfaces. These properties were found to depend on the adhesion forces of both surfaces in a differential manner, which is explained with a simple model in analogy to the Bell-Evans formalism used in dynamic force spectroscopy. The measured interaction forces between the poly(acrylic acid) chains and silicon nitride AFM tips depend on the grafting density of the polymer monolayers as well as on the contour length of the polymer chains. This study demonstrates that the stability of polymer bridges is determined by the adhesion strengths on both surfaces, which can be tuned by using pH-dependent polyelectrolyte monolayers.     

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

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

Hydrolytic behavior of enantiomeric poly(lactide) mixed monolayer films at the air/water interface: stereocomplexation effects

The Langmuir film balance technique was used to determine the hydrolytic kinetics of monolayers of the stereocomplex formed from mixtures of enantiomeric polylactides, poly(L-lactide) (L-PLA) and poly(D-lactide) (D-PLA), spread at the air-water interface. The present study investigated parameters such as degradation medium, mixture composition, and time on the relative degradation rate. The pi-A isotherms of monolayers of the mixtures provide clear evidence for the presence of a stereocomplex; the isotherms of monolayers of individual polyenantiomer show a transition at about 8.5 mN/m, whereas the transition of monolayers containing a stereocomplex formed from the equimolar mixture shifted to higher surface pressure, about 11 mN/ m. The rate of hydrolysis was recorded by a change in occupied area when the monolayer is maintained at a constant surface pressure. The hydrolysis of the mixture monolayers under basic conditions was slower than that of individual polyenantiomer monolayers, depending on the composition or the degree of complexation. In the presence of proteinase K, the enzymatic hydrolysis rate of mixture monolayers with >50 mol % l-PLA was much slower than that of the single-component L-PLA monolayer. The monolayers formed from mixtures with < or =50 mol % L-PLA did not show any change of occupied areas. This result is explained by the inactivity of D-PLA and stereocomplexed chains to the enzyme. From both results, it can be concluded that the retardation of the hydrolysis of mixture monolayers is mainly due to a strong interaction between D- and L-lactide unit sequences, which prevents the penetration of water or enzyme into the bulk.     

Degradation behaviors of polyester monolayers at the air/water interface: Alkaline and enzymatic degradations

The degradation kinetics of Langmuir monolayer films of a series of biodegradable polyesters has been studied to investigate the effect of degradation medium, alkalinity and enzymes. The degradation behavior of polyester monolayers strongly depended on both degradation medium and surface pressure. As the surface pressure was increased, the degradation rates of poly(l-lactide) (PLLA) and poly[(R)-3-hydroxybutyrate] (P(3HB)) increased in both degradation media. When monolayers were exposed to an alkaline subphase, the degradation of PLLA monolayers occurred at relatively low surface pressures; the PLLA monolayers were hydrolyzed at pH 10.5 regardless of surface pressure, while the alkaline degradation of P(3HB) monolayer occurred over a constant surface pressure of 7 mN/m at pH 11.8. These results have been explained by the difference in hydrophilic/hydrophobic balance of the polymers; PLLA is more hydrophilic than P(3HB). In contrast, the enzymatic degradations of both polymer monolayers occurred at higher constant surface pressures than those of the alkaline treatment; 7 mN/m for PLLA and 10 mN/m for P(3HB). This behavior was attributed to the enzymes being much larger than the alkaline ions: the enzymes need a larger contact area with the submerged monolayers to be activated.     

Equilibrium and dynamics of Langmuir monolayers when the interface is a selective solvent: Polystyrene-b-poly(t-butyl acrylate) block copolymers

The surface pressure of monolayers of insoluble diblock copolymers has been measured. One of the blocks is made of poly(t-butyl acrylate) (PtBA), and the other one by polystyrene (PS). The interface is a good solvent for PtBA, while it is a poor solvent for PS. For the sake of comparison, monolayers of a PtBA homopolymer (good solvent conditions) and of poly(4-hydroxy styrene) (P4HS) (poor solvent conditions) have been also measured. It has been found that the relative length of the blocks plays an important role on the shape of the surface pressure Pi versus surface concentration Gamma curves and also on the shape of the equilibrium compressibility versus Gamma curves. However, it does not affect the maximum value of Pi reached at high Gamma's. Surprisingly, the ellipsometric thickness of the copolymer monolayers is almost independent of the relative length of the blocks. The dynamics of the monolayers has been studied by step compression and by surface-light scattering techniques. When M(w,PtBA) > M(w,PS) single exponential relaxations are observed. However, stretched exponentials are obtained for M(w,PS) > or = M(w,PtBA). The relaxation times decrease with increasing Gamma for all the copolymers studied. This is the behavior usually found for poor solvent conditions (P4HS) and opposite to that found for homopolymers under good solvent conditions [PtBA, poly(vinylacetate)]. This means that the solvent quality of the interface does not determine the pressure dependence of tau. The elasticity modulus of the monolayers in the kilohertz range takes values that are similar to those of the high-frequency limit of the relaxation experiments. This means that the relaxation processes have characteristic frequencies below 1 Hz.     

Poly(ethylene oxide)s hydrophobically modified. Adsorption and spreading at the air-water interface

A comparative study of spread and adsorbed monolayer of poly(ethylene oxide)s of different molecular weight hydrophobically modified with alkyl isocyanates of different length chain is reported. The modification of the polymer was carried out according to reported procedures. The polymers obtained were studied at the air-water interface by Langmuir isotherms for spread monolayers and by Gibbs isotherms for the adsorption process. Isotherms obtained are interpreted in terms of the hydrophobic and hydrophilic balance of the polymers. Limiting area per repeating unit (A(0)) and collapse pressure (pi(c)) from spread monolayers were obtained. Spread monolayers of the hydrophobically modified polymers show larger collapse pressure values than unmodified polymer monolayers. In the adsorption process the excess surface concentration Gamma(infinity), area per repeat unit sigma, and efficiency of the adsorption were determined. The values of the area occupied per repeat unit in adsorbed monolayer (sigma) were larger than those of the spread monolayer. The efficiency of the adsorption of poly(ethylene oxide)s increases with the hydrophobic modification and with the alkyl chain length.     

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.     

Ideal spread monolayer and multilayer formation of fully hydrophobic polythiophenes via liquid crystal hybridization on water

The spread monolayer formation of hydrophobic poly(3-alkylthiophene)s (P3ATs), regioregular poly(3-hexylthiophene) ( HT-P3HT), regioregular poly(3-dodecylthiophene) ( HT-P3DT), and regioirregular poly(3-hexylthiophene) ( RI-P3HT), were attained on the water surface via cospreading with a liquid-crystal molecule, 4'-pentyl-4-cyanobiphenyl (5CB). The spread monolayers were characterized by pi- A isotherms, Brewster angle microscopy (BAM), and atomic force microscopy (AFM). The molecular area for the cospread mixtures of P3ATs and 5CB expanded more than that of pure P3ATs as shown from the pi-A isotherms. BAM revealed that the mixed film forms the monomolecularly uniform and flat films on water. AFM elucidated that the spread monolayer of the hydrophobic P3ATs formed on the top of the 5CB monolayer on water with thicknesses of ca. 1.6 and ca. 2.6 nm for the two P3HTs and HT-P3DT, respectively. The P3AT/5CB hybrid monolayers could be fully transferred onto a solid substrate, and pure P3AT monolayers were obtained after volatilization of 5CB by gentle heating. The multilayer formation of pure P3AT monolayers was prepared by layer-by-layer deposition involving repeating horizontal deposition and successive volatilization of 5CB. Grazing angle incidence X-ray diffraction measurements showed that the lamella plane of the P3ATs is perfectly oriented parallel to the substrate plane in the resulting thin films. This shows a marked contrast with those obtained by spin casting using the identical polymer, where both in-plane and out-of-plane lamellae are involved. These thin films with perfectly controlled lamella orientation should be of great significance as the model system for evaluating the charge mobility for organic polymer electric devices.     

Elastic bounded diffusion and electron propagation: dynamics of the wiring of a self-assembly of immunoglobulins bearing terminally attached ferrocene poly(ethylene glycol) chains according to a spatially controlled organization.

Molecular monolayers of immunoglobulins bearing terminally attached ferrocene poly(ethylene glycol) chains (IgG-PEG-Fc) were self-assembled at an electrode surface in a step-by-step manner involving antigen-antibody recognition reactions. The total number N of assembled IgG-PEG-Fc monolayers and the number of spacers n(i) separating two successive IgG-PEG-Fc monolayers were controlled and varied. Electron transport through the protein assembly involves the dynamics of the terminally attached PEG chains and isotopic electron exchange between ferrocene heads belonging to successive IgG-PEG-Fc monolayers. The model of elastic bounded diffusion enabled us to analyze quantitatively the dependence of the rate of electron transport on N, n(i), and the rate constant (k(e)) of isotopic electron exchange. Wiring of a molecular monolayer of redox enzyme is also quantitatively characterized.     

Carboxybetaine methacrylate polymers offer robust, long-term protection against cell adhesion

Films of poly(carboxybetaine methacrylate), poly(CBMA), grafted onto microetched gold slides are effective in preventing nonspecific adhesion of cells of different types. The degree of adhesion resistance is comparable to that achieved with the self-assembled monolayers, SAMs, of oligo(ethylene glycol) alkanethiolates. In sharp contrast to the SAMs, however, substrates protected with poly(CBMA) can be stored in dry state without losing their protective properties for periods up to 2 weeks.     

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

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

High-capacity binding of proteins by poly(acrylic acid) brushes and their derivatives

Polymeric coatings with high protein-binding capacities are important for increasing the output of affinity-based protein purification and decreasing the detection limits of antibody microarrays. This report describes the use of thick poly(acrylic acid) (PAA) brushes to immobilize as much as 80 monolayers of protein. The brushes were prepared using a recently developed procedure that allows polymerization of 100-nm-thick poly(tert-butyl acrylate) films from a surface in just 5 min along with hydrolysis of these films to PAA in 15 min. Covalent binding of bovine serum albumin (BSA) to PAA brushes that were activated using standard coupling agents, however, resulted in immobilization of less than two monolayers of BSA because of competitive hydrolysis of the esters in the activated film. In contrast, derivatization of PAA with nitrilotriacetate (NTA)-Cu2+ complexes yielded films capable of binding many monolayers of protein via metal-ion affinity interactions. For example, derivatization of 55-nm-thick PAA films with NTA-Cu2+ allowed immobilization of about 15 monolayers (5.8 microg/cm2 or 58 nm) of BSA. The binding capacity was even higher for myoglobin (7.7 microg/cm2) and anti-IgG (9.6 microg/cm2). Remarkably, electrostatic adsorption of lysozyme in 55-nm-thick, underivatized PAA resulted in as much as 80 monolayers (16.2 microg/cm2 or 162 nm) of adsorbed protein. Polymer synthesis, derivatization, and swelling, as well as BSA immobilization kinetics and thermodynamics were characterized using reflectance FT-IR spectroscopy, ellipsometry, and protein assays.     

Monolayers of hydrogen-bonded polymer blends at the air–water interface: poly(vinylacetate)+poly (4-hydroxystyrene)

 The surface pressure (Π) vs surface concentration (Γ_s) curves of the hydrogen-bonded polymer blend poly(vinylacetate)+ poly(4-hydro-xystyrene) (PVAc+P4HS) have been measured at 25 °C onto a water subphase at pH=2.0. While PVAc forms extended monolayers, and the free surface of water is found to be a good solvent for it, P4HS forms compressed monolayers, and the surface is a near Θ-type solvent for it. PVAc and P4HS form miscible non-ideal monolayers until near the collapse pressure through the whole concentration range. The composition dependence of the Π–Γ_s curves is rather complex. Contrary to what might be expected, the addition of PVAc to the blend does not reduce the rigidity of the monolayer until its weight fraction is larger than 0.5. The compressibility data of the P4HS-rich monolayers suggest the existence of a second maximum at high surface coverages, a result already observed in some polysiloxanes. Received: 11 March 1998 Accepted: 7 May 1998     

Rheological behavior of precursor PPV monolayers

The rheological behavior of different precursor poly(p-phenylene vinylene) (prec-PPV) monolayers at the air-water interface was investigated using an interfacial stress rheometer (ISR). This device nicely reveals a transition of the precursor poly(2,5-dimethoxy-1,4 phenylene vinylene) (prec-DMePPV) monolayer from Newtonian to elastic behavior with increasing surface pressure. The transition is accompanied by an increase in the modulus. This behavior coincides with the coagulation of different 2D condensed domains as revealed by Brewster angle microscopy (BAM). However, partly converted prec-DMePPV monolayers show elastic behavior even at low surface pressures, although a sudden increase of the moduli does occur. This phenomenon is attributed to enhanced hydrophobic interactions between the conjugated moieties in the partly converted polymers. The latter also explains the stretching behavior of the partly converted prec-DMePPV upon transfer in Langmuir-Blodgett-type vertical dipping. The increase of the moduli which is observed is much more gradual in the precursor poly(2,5-dibutoxy-1,4-phenylene vinylene), prec-DBuPPV, a monolayer which is in agreement with the expected expanded state of the latter monolayer.