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A new study uses optical activity to investigate the amorphous solid state of polymer glasses.

The article reports that tethering rodlike polymers onto solid surfaces by their chain ends with a moderate grafting density can result to a liquid crystalline monolayer of planar-oriented rods. It is emphasized that the approach to the liquid crystalline self-assembled monolayers may be used to design well-ordered monolayers of rodlike polymers with several functionalities.

Monolithic molecular separation membranes were prepared by utilizing concentration polarization-induced gelation of a particulate covalent network on a porous support. Polymerization of tetra-amine and di-isocyanate monomers produced a stable dispersion of nanoparticles of urea-bonded networks in organic solvent. As the sols were allowed to pass through the support, the critical gelation point was reached due to concentration polarization via accumulation of relatively larger network particles on the substrate surface, resulting in deposition of a nanoporous gel layer, which, upon drying, turned to a monolithic layer of a covalent network with interconnected pores estimated to be 2-10 nm wide. The resulting membrane filters off solutes larger than 3 nm. Facile control of the structure and thickness of the active layer along with the superior chemical and thermal stability are promising features for solvent-resistant nanofiltration membranes suitable for separation of organic, as well as aqueous, solution mixtures.

We demonstrated that the layer-by-layer growth of thin film crystals of conjugated organic molecules is facilitated by their hydrogen-bonding capabilities. We synthesized bis(3-hydroxypropyl)-sexithiophene (bHP6T), which includes two hydroxyalkyl groups that promote interlayer and intermolecular molecular interactions during the crystal growth process. Under the optimal deposition conditions, the crystals grew in a nearly perfect layer-by-layer mode on the solid substrate surfaces, enabling the formation of uniform charge transporting films as thin as a few monolayers. A thin film transistor device prepared from a bHP6T film only 9 nm thick exhibited a charge carrier mobility well above 1 × 10(-2) cm(2)/(V s) and an on/off ratio exceeding 1 × 10(4). These properties are better than the properties of other sexithiophene-based devices yet reported. The devices exhibited enhanced stability under atmospheric conditions, and they functioned properly, even after storage for more than 2 months.

An aqueous vesicular system that is switchable by electric potential without addition of any chemical redox agents into the solution is demonstrated using redox-responsive self-assembly of an amphiphilic rod-coil molecule consisting of a tetraaniline and a poly(ethylene glycol) block. The vesicle membrane is split by an oxidizing voltage into smaller pucklike micelles that can reassemble to form vesicles upon exposure to a reducing voltage. The switching mechanism is explained by the packing behavior of the tetraaniline units constituting the membrane core, which depends on their oxidation states., (© 2011 American Chemical Society)

Monolayers of 1,1'-bi-2-naphthol (BN) derivatives, of which the two naphthalene rings are twisted along the carbon(1)-carbon(1') single bond, were studied for their conformational effect on the growth of pentacene crystals on their monolayer surface. BN monolayers with H and Br at 6,6'-positions (H-BN and Br-BN) were prepared by immersion-coating in toluene solution of the corresponding BNSiCl2. Pentacene was thermally evaporated onto the H-BN and Br-BN monolayers, silica, octadecylsilyl (ODTS) SAM, and a micropattern of H-BN and ODTS SAM. Pentacene crystals were also grown on the SAMs of 1-naphthylsilyl(NPh), phenylsilyl(Ph), and diphenylsilyl (DPh) groups, which are aromatic and have contact angle values similar to those of the the BN monolayers. AFM images of the crystals at the early stage of growth indicated that the BN monolayers suppressed the nucleation while facilitating the growth of nuclei to larger crystals. The low nucleation density and high growth rate are accounted for by the amorphous nature of the twisted BN monolayer surface where the intermolecular interaction between neighboring adsorbates is likely to be suppressed. The results offer new insights into designing surfaces for controlling the crystallization kinetics of organic materials.

A block copolymer containing a rodlike block is studied for its adsorption and formation of nanostructured thin films on the substrate surface. The block copolymer is poly(styrene-b-3-triethoxysilylpropylisocyanate) (PS-b-PIC) of which the PIC chain consists of repeating amide units with triethoxysilyl side groups. As the copolymer chains are adsorbed onto silica surfaces, the PIC blocks pack laterally on the plane in a smectic manner, and the PS chains segregate along the ordered PIC chains, resulting in stripe patterns. The width of the stripes formed on the silica surface appeared to be much larger that on the carbon surface. This was accounted for by the bilayered smectic packing of the rod blocks that is induced by rod-surface attractive interaction. The periodicity of the stripe pattern on the carbon surface indicates that interdigitated packing is preferred by the copolymers on the hydrophobic surface in a manner similar to those in the bulk state of rod-coils. Excess rod-coils on the bilayered smectic layer resulted in a terraced morphology due to large difference in the periodicity between the bilayered smectic layer at the substrate surface and the interdigitated smectic layer in the bulk.

A diblock copolymer consisting of poly(3-(triethoxysilyl)propylisocyanate) (PIC) and polystyrene(PS) was synthesized by anionic polymerization. A polymeric monolayer of the block copolymer was formed on silica substrates by various grafting techniques such as immersion, casting, or contact-printing. The PIC block adheres covalently to Si substrates in an in-plane fashion due to its extended rodlike conformation and reactivity to the silica. The polystyrene blocks aggregate to form mounds on the surface resulting in a new type of nanopatterned polymer brush. The self-limiting adsorption of the rod coils results in a thickness of about 5 nm regardless of the solution concentration and coating method. This particular property allowed microcontact printing directly onto silicon or glass substrates. The resulting surface morphology consisted of nanoscale domains given by the block copolymer and uniform thickness micropatterns transferred from the stamp within the printed area. This study offers a simple new method to prepare a covalent polymeric monolayer with nano- and micropatterns, which can be performed directly onto various silicon-based substrates.