New amphiphilic block copolymers S nSz m consisting of blocks with varied degrees of polymerization, n and m, of polystyrene, S, and polystyrene carrying an amphiphilic polyoxyethylene-polytetrafluoroethylene chain side-group, Sz, were prepared by controlled atom transfer radical polymerization (ATRP). The block copolymers, either alone or in a blend with commercial SEBS (10 wt% SEBS), were spin-coated in thinner films (200-400 nm) on glass and spray-coated in thicker films ( approximately 500 nm) on a SEBS underlayer (150-200 microm). Angle-resolved X-ray photoelectron spectroscopy (XPS) measurements proved that at any photoemission angle, varphi, the atomic ratio F/C was larger than that expected from the known stoichiometry. Consistent with the enrichment of the outer film surface (3-10 nm) in F content, the measured contact angles, theta, with water (theta w > or = 107 degrees ) and n-hexadecane (theta h > or = 64 degrees ) pointed to the simultaneous hydrophobic and lipophobic character of the films. The film surface tension gamma S calculated from the theta values was in the range 13-15 mN/m. However, the XPS measurements on the "wet" films after immersion in water demonstrated that the film surface underwent reconstruction owing to its amphiphilic nature, thereby giving rise to a more chemically heterogeneous structure. The atomic force microscopy (AFM) images (tapping mode/AC mode) revealed well-defined morphological features of the nanostructured films. Depending on the chemical composition of the block copolymers, spherical (ca. 20 nm diameter) and lying cylindrical (24-29 nm periodicity) nanodomains of the S discrete phase were segregated from the Sz continuous matrix (root-mean-square, rms, roughness approximately 1 nm). After immersion in water, the underwater AFM patterns evidenced a transformation to a mixed surface structure, in which the nanoscale heterogeneity and topography (rms = 1-6 nm) were increased. The coatings were subjected to laboratory bioassays to explore their intrinsic ability to resist the settlement and reduce the adhesion strength of two marine algae, viz., the macroalga (seaweed) Ulva linza and the unicellular diatom Navicula perminuta. The amphiphilic nature of the copolymer coatings resulted in distinctly different performances against these two organisms. Ulva adhered less strongly to the coatings richer in the amphiphilic polystyrene component, percentage removal being maximal at intermediate weight contents. In contrast, Navicula cells adhered less strongly to coatings with a lower weight percentage of the amphiphilic side chains. The results are discussed in terms of the changes in surface structure caused by immersion and the effects such changes may have on the adhesion of the test organisms.

Modulation of light by light as stimulus has been explored by the use of liquid-crystalline (LC) materials with photosensitive moieties. Azobenzene derivatives with monomeric and polymeric forms were prepared, which show nematic (N) LC behavior in the trans form and no LC phase in the cis isomer. Photoirradiation of a very thin film of the liquid-crystalline azobenzene derivatives (∼200 nm) in the trans form resulted in the disappearance of the N phase because of trans−cis photoisomerization of each mesogen, and the N phase recovered quickly when the irradiated sample was kept in the dark in the whole temperature range where the azobenzene LCs showed the N phase because of cis−trans thermal isomerization. Time-resolved measurements by the use of a laser pulse (355 nm, 10 ns fwhm) revealed that the N-to-isotropic (I) phase transition took place in 200 μs in both monomeric and polymeric systems. This response is at least 1 order of magnitude faster than the response of nematic LCs previously reported. , In the polymer system the N−I phase transition was also induced in 200 μs even below T g. The isotropic glass state induced by photoirradiation in the polymer sample below T g was stable at room temperature for a long period even after the trans form was restored by the thermal back-isomerization.

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Two families of narrow polydispersity poly(styrene)-based block copolymers bearing side groups containing both a phenyl ring and a para-linked semifluorinated side group were designed to produce stable low energy surfaces. The effects of the phenyl ring on the surface and bulk structure of the materials were investigated. The semifluorinated side chains were found to self-assemble into liquidcrystalline smectic layers within the microphase domains. An unexpected enhancement of surface organization by the aromatic group was observed. The bulk morphology and the interplay between microphase separation and liquid crystalline self-assembly were examined using transmission electron microscopy and X-ray scattering. Near-edge X-ray absorption fine structure (NEXAFS) studies were used to probe the surface coverage of the fluorinated segments. NEXAFS also allowed the determination of the orientation parameters (S C-F and Sπ*) of the C-F bond and phenyl ring of the semifluorinated side groups at the surface. On the basis of these data, the orientational coupling between the -CF2-helix and the aromatic ring was found to depend on the length of the fluorocarbon substituent.