Wetting behavior of oleophobic polymer coatings synthesized from fluorosurfactant-macromers.

Architecturally similar monomers were copolymerized with a water-oil discriminate fluorosurfactant to create hydrophilic-oleophobic coatings. Acrylic acid, hydroxyethyl methacrylate, and methyl methacrylate were used as comonomers with the fluorosurfactant macromer. The homopolymers of the selected comonomers are water-soluble, water-swellable, and water-insoluble, respectively, thus coupling the surfactant monomer in varying concentration within polymers of varying hydrophilicity. Wetting behavior of water and hexadecane were examined as a function of copolymer composition, thus revealing critical structure-property relationships for the surfactant-based system. Acrylic acid copolymers and hydroxyethyl methacrylate copolymers both exhibited a hexadecane contact angle which exceeded the water contact angle. This condition predicted an ability to "self-clean" oil-based foulants. The most oleophobic of the self-cleaning copolymers had an advancing hexadecane contact angle of 73° and an advancing water contact angle of 40°. It was determined that the advancing and receding water and hexadecane contact angle response varies montonically for each copolymer type as the surface concentration of the surfactant is varied. Comparing between copolymer types revealed large differences in wetting response. Methyl methacrylate copolymers with 2.8 mol % surfactant had advancing water contact angle 82° and advancing hexadecane contact angle 26°, which is neither oleophobic nor self-cleaning. In contrast, acrylic acid copolymers with 3.1 mol % surfactant had advancing water contact angle of 44° and advancing hexadecane contact angle of 52°, creating a self-cleaning coating. Thus, the nature of the comonomer exerts a greater influence than the surfactant content on the wetting behavior and self-cleaning ability of the final coating.

Impact of polymer-bound iodine on fibronectin adsorption and osteoblast cell morphology in radiopaque medical polymers: tyrosine-derived polycarbonate blends as a model system.

Imaging of polymer implants during surgical implantations is challenging in that most materials lack sufficient X-ray contrast. Synthetic derivatization with iodine serves to increase the scattering contrast but results in distinct physicochemical properties in the material which influence subsequent protein adsorption and cell morphology behavior. Herein we report the impact of increasing iodine inclusion on the cell morphology (cell area and shape) of MC3T3-E1 osteoblasts on a series of homopolymers and discrete blend thin films of poly(desaminotyrosyl tyrosine ethyl ester carbonate), poly(DTE carbonate), and an iodinated analogue poly(I(2)-DTE carbonate). Cell morphology is correlated to film chemical composition via measuring fibronectin (FN) adhesion protein adsorption profile on these films. FN exhibits up to 2-fold greater adsorption affinity for poly(I(2)-DTE carbonate) than (poly(DTE carbonate)). A correlation was established between cell area, roundness, and the measured FN adsorption profile on the blend films up to 75% by mass poly(I(2)-DTE carbonate). Data suggest that incorporation of iodine within the polymer backbone has a distinct impact on the way FN proteins adsorb to the surface and within the studied blend systems; the effect is composition dependent.

Langmuir-Blodgett monolayers of gold nanoparticles with amphiphilic shells from V-shaped binary polymer arms.

Gold nanoparticles functionalized with amphiphilic polybutadiene-poly(ethylene glycol) (PB-PEG) V-shaped arms formed stable Langmuir monolayers at the air-water and the air-solid interfaces. At these interfaces, the binary arms vertically segregated into a dense polymer corona, which surrounded the gold nanoparticles, preventing their large-scale agglomeration and keeping individual nanoparticles well-separated from each other and forming flattened, pancake nanostructures. The presence of both PEG and PB chains in the close proximity to the gold core was confirmed by surface enhanced Raman spectroscopy, whereas the AFM phase contrast images revealed the presence of 2 nm gold cores surrounded by the polymer shell with the diameter of 11 nm. We suggest that the amphiphilic shell drives their spontaneous organization into discrete 2D pancake-like hybrid structures that measured up to 10 microm in diameter and had a high packing density of gold clusters.

Surface morphologies of Langmuir-Blodgett monolayers of PEOnPSn multiarm star copolymers.

Star polymers composed of equal numbers of poly(ethylene oxide) (PEO) and polystyrene (PS) arms with variable lengths and a large (up to 38 total) number of arms, PEO(n)PS(n), have been examined for their ability to form domain nanostructures at the air-water and air-solid interfaces. All PEO(n)PS(n) star polymers formed stable Langmuir-Blodgett (LB) monolayers transferable to a solid substrate. A range of nanoscale surface morphologies have been observed, ranging from cylindrical to circular domains to bicontinuous structures as the weight fraction of the PEO block varied from 19% to 88% and n from 8 to 19. For the PS-rich stars and at elevated surface pressure, a two-dimensional supramolecular netlike nanostructure was formed. In contrast, in the PEO-rich star polymer with the highest PEO content, we observed peculiar dendritic superstructures caused by intramolecular segregation of nonspherical core-shell micellar structures. On the basis of Langmuir isotherms and observed monolayer morphologies, three different models of possible surface behavior of the star polymers at the interfaces were proposed.

Assembling of dense fluorescent supramolecular webs via self-propelled star-shaped aggregates.

We report a novel mechanism of assembly of dendronized rod molecules into a dense supramolecular fluorescencent web featuring self-propelled mechanistic inward motion of star-shaped aggregates within a solution droplet. We suggest that such a motion (observed in real time) is caused by the self-repulsion of the growing star-shaped nuclei from the liquid-solid-air interface in the course of one-dimensional growth of the anchored arms. An intriguing mechanism discovered here involves microscopic (hundred micrometers) directional motion of the microscopic aggregates driven by one-dimensional molecular assembly, which opens a new venue for guided assembly of dense mesoscopic supramolecular webs. Such assemblies can serve as interesting microfluidic networks, a web of optical switches, and model systems for studying intercellular communication.

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.

Amphiphilic treelike rods at interfaces: layered stems and circular aggregation.

Amphiphilic dendron-rod molecules with three hydrophilic poly(ethylene oxide) (PEO) branches attached to a hydrophobic octa-p-phenylene rod stem were investigated for their ability to form two-dimensional micellar structures on a solid surface. A treelike shape of the molecules was reported to be a major factor in the formation of nonplanar micellar structures in solution and in the bulk state (cylindrical and spherical). We observed that in these treelike amphiphilic molecules the hydrophilic terminated dendron branches assemble themselves in surface monolayers with the formation of two-dimensional layered or circular micellar structures. We suggested the formation of the planar ribbon-like structures with interdigitated layering within the loosely packed monolayers and circular, ringlike structures (2D circular aggregates) in the precollapsed state.

Langmuir and grafted monolayers of photochromic amphiphilic monodendrons of low generations.

Four generations of monodendrons with multiple dodecyl alkyl tails (AA-N, N representing number of alkyl tails from 1 to 8), an azobenzene spacer group, and a carboxylic acid polar head have been studied at the air-water and air-solid interface using AFM, GIXD, X-ray reflectivity, and UV-vis spectrometry. The one and two tail molecules formed orthorhombic lateral packing with long-range intramonolayer ordering. Good agreement between molecular models and thickness measurements indicated that the one and two tail molecules orient along the surface normal. The increase in the cross-sectional mismatch caused by the presence of the multiple chains for the higher generations disrupted the long-range ordering and forced the alkyl tails to adopt quasi-hexagonal structure. The higher generations (AA-4 and AA-8) formed a kinked structure with the alkyl tails oriented perpendicular to the surface with the azobenzene group tilted at a large degree toward the surface. The photoisomerization behavior in dilute solutions, at the air-water interface, and for grafted layers demonstrated that lower generation monodendrons maintained the photochromic behavior after chemical grafting to the silicon substrates, although the confinement of the molecules in monolayers significantly increased the reorganization time.

Interfacial micellar structures from novel amphiphilic star polymers.

An amphiphilic heteroarm star polymer containing 12 alternating hydrophobic/hydrophilic arms of polystyrene (PS) and poly(acrylic acid) (PAA) connected to a well-defined rigid aromatic core was studied at the air-water and the air-solid interfaces. At the air-water interface, the molecules spontaneously form pancakelike micellar aggregates which measure up to several microns in diameter and 5 nm in thickness. Upon reduction of the surface area per molecule to 7 nm2, the two-dimensional micelles merged into a dense monolayer. We suggest that confined phase separation of dissimilar polymer arms occurred upon their segregation on the opposite sides of the rigid disklike aromatic core, forcing the rigid cores to adopt a face-on orientation with respect to the interface. Upon transfer onto solid supports the PS chains face the air-film interface making it completely hydrophobic, and the PAA chains were found to collapse and form a thin flattened underlayer. This study points toward new strategies to create large 2D microstructures with facial amphiphilicity and suggests a profound influence of star molecular architecture on the self-assembly of amphiphiles at the air-water interface.

Assembling of amphiphilic highly branched molecules in supramolecular nanofibers.

We found that the amplification of weak multiple interactions between numerous peripheral branches of irregular, flexible, polydisperse, and highly branched molecules can facilitate their self-assembly into nanofibrillar micellar structures at solid surfaces and the formation of perfect long microfibers in the course of crystallization from solution. The core-shell architecture of the amphiphilic dendritic molecules provides exceptional stability of one-dimensional nanofibrillar structures. The critical condition for the formation of the nanofibrillar structures is the presence of both alkyl tails in the outer shell and amine groups in the core/inner shell. The multiple intermolecular hydrogen bonding and polar interactions between flexible cores stabilize these nanofibers and make them robust albeit flexible. This example demonstrates that one-dimensional supramolecular assembling at different spatial scales (both nanofibers and microfibers) can be achieved without a tedious, multistep synthesis of shape-persistent molecules.