A facile templated synthesis of functional nanocarbon materials with well-defined spherical mesopores is developed using all-organic porogenic precursors comprised of hairy nanoparticles with nitrogen-rich polyacrylonitrile shells grafted from sacrificial cross-linked poly(methyl methacrylate) cores (xPMMA-g-PAN). Such shape-persistent all-organic nanostructured precursors, prepared using atom transfer radical polymerization (ATRP), assure robust formation of template nanostructures with continuous PAN precursor matrix over wide range of compositions, and allow for removal of the sacrificial template through simple thermal decomposition. Carbon materials prepared using this method combine nitrogen enrichment with hierarchical nanostructure comprised of microporous carbon matrix interspersed with mesopores originating from sacrificial xPMMA cores, and thus perform well as CO₂ adsorbents and as supercapacitor electrodes.

We demonstrate a simple bioconjugate polymer system that undergoes reversible self-assembling into extended fibrous structures, reminiscent of those observed in living systems. It is comprised of green fluorescent protein (GFP) molecules linked into linear oligomeric strands through click step growth polymerization with dialkyne poly(ethylene oxide) (PEO). Confocal microscopy, atomic force microscopy, and dynamic light scattering revealed that such strands form high persistence length fibers, with lengths reaching tens of micrometers, and uniform, sub-100 nm widths. We ascribe this remarkable and robust form of self-assembly to the cooperativity arising from the known tendency of GFP molecules to dimerize through localized hydrophobic patches and from their covalent pre-linking with flexible PEO. Dissipative particle dynamics simulations of a coarse-grained model of the system revealed its tendency to form elongated fibrous aggregates, suggesting the general nature of this mode of self-assembly.

Thermoresponsive hydrogels with efficient water-release channels were prepared by incorporating star-shaped macromolecular pore precursors, with degradable disulfide crosslinked cores and hydrophilic poly(ethylene oxide) (PEO) arms, into the gel network. The gel framework exhibiting lower critical solution temperature (LCST) behavior was synthesized by atom transfer radical polymerization (ATRP) of 2-(2-methoxyethoxy)ethyl methacrylate and ethylene glycol dimethacrylate. The incorporation of degradable star macromolecules (dSM) was facilitated by growing the gel from ATRP initiator sites contained within their cores. Following the formation of the gel, the dSM cores were degraded, yielding uniform pores lined with hydrophilic PEO chains. The effect of hydrophilic pores on thermoresponsive hydrogel performances was studied by comparing hydrogels containing hydrophilic pores with analogous hydrogels with neutral pores or with pore-free controls. Dye absorption/release experiments pointed to the suitability of newly synthesized hydrogels as controlled-release media, for example, for drug delivery. Cell culture experiments confirmed their nontoxicity and biocompatibility (cell viability>98 %).

The planarization of bottom-contact organic field-effect transistors (OFETs) resulting in dramatic improvement in the nanomorphology and an associated enhancement in charge injection and transport is reported. Planar OFETs based on regioregular poly(3-hexylthiophene) (rr-P3HT) are fabricated wherein the Au bottom-contacts are recessed completely in the gate-dielectric. Normal OFETs having a conventional bottom-contact configuration with 50-nm-high contacts are used for comparison purpose. A modified solvent-assisted drop-casting process is utilized to form extremely thin rr-P3HT films. This process is critical for direct visualization of the effect of planarization on the polymer morphology. Atomic force micrographs (AFM) show that in a normal OFET the step between the surface of the contacts and the gate dielectric disrupts the self-assembly of the rr-P3HT film, resulting in poor morphology at the contact edges. The planarization of contacts results in notable improvement of the nanomorphology of rr-P3HT, resulting in lower resistance to charge injection. However, an improvement in field-effect mobility is observed only at short channel lengths. AFM shows the presence of well-ordered nanofibrils extending over short channel lengths. At longer channel lengths the presence of grain boundaries significantly minimizes the effect of improvement in contact geometry as the charge transport becomes channel-limited.