Impact of charge switching stimuli on supramolecular perylene monoimide assemblies.

The development of stimuli-responsive amphiphilic supramolecular nanostructures is an attractive target for systems based on light-absorbing chromophores that can function as photosensitizers in water. We report here on a water soluble supramolecular carboxylated perylene monoimide system in which charge can be switched significantly by a change in pH. This was accomplished by substituting the perylene core with an ionizable hydroxyl group.

Molecular Control of Internal Crystallization and Photocatalytic Function in Supramolecular Nanostructures.

Supramolecular light-absorbing nanostructures are useful building blocks for the design of next-generation artificial photosynthetic systems. Development of such systems requires a detailed understanding of how molecular packing influences the material's optoelectronic properties. We describe a series of crystalline supramolecular nanostructures in which the substituents on their monomeric units strongly affects morphology, ordering kinetics, and exciton behavior.

Mimicking the Bioactivity of Fibroblast Growth Factor-2 Using Supramolecular Nanoribbons.

Fibroblast growth factor (FGF-2) is a multifunctional growth factor that has pleiotropic effects in different tissues and organs. In particular, FGF-2 has a special role in angiogenesis, an important process in development, wound healing, cell survival, and differentiation. Therefore, incorporating biological agents like FGF-2 within therapeutic biomaterials is a potential strategy to create angiogenic bioactivity for the repair of damaged tissue caused by trauma or complications that arise from age and/or disease.

Crystal-Phase Transitions and Photocatalysis in Supramolecular Scaffolds.

The energy landscape of a supramolecular material can include different molecular packing configurations that differ in stability and function. We report here on a thermally driven crystalline order transition in the landscape of supramolecular nanostructures formed by charged chromophore amphiphiles in salt-containing aqueous solutions. An irreversible transition was observed from a metastable to a stable crystal phase within the nanostructures.

Direct exfoliation of graphite to graphene in aqueous media with diazaperopyrenium dications.

The 2,9-dimethyldiazaperopyrenium dication can be made from a ubiquitous and inexpensive feedstock in three simple steps as its chloride salt. When mixed with powdered graphite at 23 °C, this behemoth of a molecular compound exfoliates graphite to graphene in water under mild conditions.

Nanoscale elastic modulus variation in loaded polymeric micelle reactors.

Tapping mode atomic force microscopy (TM-AFM) enables mapping of chemical composition at the nanoscale by taking advantage of the variation in phase angle shift arising from an embedded second phase. We demonstrate that phase contrast can be attributed to the variation in elastic modulus during the imaging of zinc acetate (ZnAc)-loaded reverse polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) diblock co-polymer micelles less than 100 nm in diameter. Three sample configurations were characterized: (i) a 31.

Grooved nanowires from self-assembling hairpin molecules for solar cells.

One of the challenges facing bulk heterojunction organic solar cells is obtaining organized films during the phase separation of intimately mixed donor and acceptor components. We report here on the use of hairpin-shaped sexithiophene molecules to generate by self-assembly grooved nanowires as the donor component in bulk heterojunction solar cells. Photovoltaic devices were fabricated via spin-casting to produce by solvent evaporation a percolating network of self-assembled nanowires and fullerene acceptors.

Solution-processed LiF for work function tuning in electrode bilayers.

Although ambient processing is the key to low-cost organic solar cell production, high-vacuum thermal evaporation of LiF is often a limiting step, motivating the exploration of solution processing of LiF as an alternative electrode interlayer. Submonolayer films are realized with the assistance of polymeric micelle reactors that enable LiF particle deposition with controlled nanoscale surface coverage. Scanning Kelvin probe reveals a work function tunable with nanoparticle coverage with higher values than that of bare indium tin oxide (ITO).

Determining the morphology of polystyrene-block-poly(2-vinylpyridine) micellar reactors for ZnO nanoparticle synthesis.

We report the use of reverse PS-b-P2VP diblock copolymer micelles as true nanoscale-sized reactor vessels to synthesize ZnO nanoparticles. The reverse micelles were formed in toluene and then sequentially loaded with zinc acetate dihydrate and tetramethylammonium hydroxide reactants. Moreover, high spatial resolution Z-contrast imaging and EDX spectroscopy techniques were used to confirm the segregation of the Zn cation to the core of the loaded micelles.

Nanoscale composition mapping of segregation in micelles with tapping-mode atomic force microscopy.

Under energy-dissipative cantilevered tip-sample interaction, phase imaging using tapping-mode atomic force microscopy enables compositional mapping of composites containing a harder inorganic phase at the nanometer scale, embedded in a polymer matrix. The contrast in the phase images is shown to be dependent on the variation in the elastic properties of the diblock copolymer reverse micelles loaded with zinc acetate. Tapping conditions are also shown to determine whether the contrast is positive or negative for the harder core of the loaded micelles, based on the competition between attractive and repulsive tip-sample interaction forces.