Tethered membranes have been proven during recent years to be a powerful and flexible biomimetic platform. We reported in a previous article on the design of a new architecture based on the self-assembly of a thiolipid on ultrasmooth gold substrates, which shows extremely good electrical sealing properties as well as functionality of a bilayer membrane. Here, we describe the synthesis of lipids for a more modular design and the adaptation of the linker part to silane chemistry. We were able to form a functional tethered bilayer lipid membrane with good electrical sealing properties covering a silicon oxide surface. We demonstrate the functional incorporation of the ion carrier valinomycin and of the ion channel gramicidin.

Polystyrene (PS)/poly(ethylene oxide) (PEO) amphiphilic star-block copolymers and dendrimer-like architectures were prepared using a core-first method. PS stars were first obtained by atom transfer radical polymerization using three and four functional benzyl halides. The chain ends of these star polymers were subsequently modified to generate either the same or twice the number of hydroxyl groups that served to grow the PEO blocks by anionic polymerization of ethylene oxide. Well-defined PS n-b-PEOn (n ) 3 or 4) stars and PS3-b-PEO6 dendrimer-like copolymers exhibiting a monomodal and narrow molar mass distribution were obtained in this way. When spread at the air/water interface, these stars proved to be surface active, forming stable reproducible films. Isotherms yielded A 0 (theoretical surface area occupied by a film at zero pressure) values, allowing for quantitative comparisons between the stars and linear diblock analogues. Both structures demonstrated similar behavior, passing from liquid expanded regions to highly compressed structures at comparable molecular areas.

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The effect of magnetic fields on the orientation and properties of 4,4'-bis(2,3-epoxypropoxy)-alpha-methylstilbene cured with sulfanilamide has been studied. This epoxy system is initially isotropic and forms a smectic A phase upon curing. A magnetic field was applied during the cure reaction, resulting in alignment of the molecules along the direction of the applied field. Measurement of the orientation parameter of the fully cured material by wide-angle X-ray scattering (WAXS) showed that orientation improved with an increase in field strength. The orientation parameters of the smectic layer normals calculated from the inner reflection of the WAXS pattern attained a maximum level of approximately 0.8 at a field strength of approximately 12 T. The orientation parameters calculated from the outer reflection of the WAXS pattern were considerably lower, possibly due to the presence of amorphous regions associated with domain boundaries or the loss of molecular alignment within the smectic layers due to topological restrictions of the cross-linking sites. Orientation resulted in an anisotropic linear thermal expansion coefficient after curing, although the overall volumetric expansion was constant. The elastic tensile modulus increased with the square of the orientation parameter, attaining a maximum value of 8.1 GPa, compared to 3.1 GPa for the unoriented material. The change in modulus with orientation could be fit with a simple model for the modulus of anisotropic materials.

A series of three-arm star block copolymers were examined using atomic force microscopy (AFM). These stars consisted of a polystyrene core composed of ca. 111 styrene units/branch with poly(ethylene oxide) (PEO) chains at the star periphery. Each star contained different amounts of PEO, varying from 107 to 415 ethylene oxide units/branch. The stars were spread as thin films at the air/water interface on a Langmuir trough and transferred onto mica at various surface pressures. Circular domains representing 2D micelle-like aggregated molecules were observed at low pressures. Upon further compression, these domains underwent additional aggregation in a systematic manner, including micellar chaining. At this point, domain area and the number of molecules/domain increased with increasing pressure. In addition, it was found that longer PEO chains led to greater intermolecular separation and less aggregation. These AFM results correspond to attributes seen in the surface pressure-area isotherms of the stars. In addition, they demonstrate the viability of AFM as a quantitative characterization technique.

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Using a water-in-oil microemulsion system, silica nanoparticles containing superparamagnetic iron oxide (SPIO) crystals have been prepared and characterized. With this method, the loading of iron oxide crystals, the thickness of the silica shells, and the overall particle sizes are tunable. Moving from low to high water concentration, within the microemulsion region, resulted in a gradual shift from larger particles, ca. 100 nm and fully loaded with SPIOs, to smaller particles, ca. 30 nm containing only one or a few SPIOs. By varying the amount of silica precursor, the thickness of the silica shell was altered. Field dependent magnetization measurements showed the magnetic properties of the SPIOs were preserved after the synthesis.

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