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. In acidic environments, crystalline supramolecular nanoribbons with dimensions on the order of 500 × 50 × 2 nm form readily, while in basic solution the additional electrostatic repulsion of the ionized hydroxyl reduces assemblies to very small dimensions on the order of only several nanometers. The HOMO/LUMO levels were also found to be sensitive to pH; in acidic media the HOMO/LUMO levels are -5.65 and -3.70 eV respectively versus vacuum, whereas is in basic conditions they are -4.90 and -3.33 eV, respectively. Utilizing the assemblies as photosensitizers in photocatalytic production of hydrogen with [Mo3S13]2- as a catalyst at a pH of 4, H2 was generated with a turnover number of 125 after 18 hours. Charge switching the assemblies at a pH of 9-10 and using an iron porphyrin catalyst, protons could again be reduced to hydrogen and CO2 was reduced to CO with a turnover number of 30. The system investigated offers an example of dynamic photosensitizing assemblies that can drive reactions in both acidic and basic media.

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. By designing constitutionally-isomeric perylene monoimide (PMI) amphiphiles, the effect of side chain sterics on nanostructure crystallization was studied. Molecules with short amine linked alkyl-tails rapidly crystallize upon dissolution in water, while bulkier tails require the addition of salt to screen electrostatic repulsion and annealing to drive crystallization. A PMI monomer bearing a 3-pentylamine tail was found to possess a unique structure that results in strongly red-shifted absorbance, indicative of charge-transfer exciton formation. This particular supramolecular structure was found to have an enhanced ability to photosensitize a thiomolybdate, [(NH4)2Mo3S13], catalyst to generate hydrogen gas.

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. However, the use of growth factors as therapeutic agents can be costly and does not always bring about efficient tissue repair due to rapid clearance from the targeted site. An alternative would be a stable supramolecular nanostructure with the capacity to activate the FGF-2 receptor that can also assemble into a scaffold deliverable to tissue. We report here on peptide amphiphiles that incorporate a peptide known to activate the FGF-2 receptor and peptide domains that drive its self-assembly into supramolecular nanoribbons. These FGF2-PA nanoribbons displayed the ability to increase the proliferation and migration of the human umbilical vein endothelial cells (HUVECs) in vitro to the same extent as the native FGF-2 protein at certain concentrations. We confirmed that this activity was specific to the FGFR1 signaling pathway by tracking the phosphorylation of downstream signaling effectors such ERK1/2 and pH3. These results indicated the specificity of FGF2-PA nanoribbons in activating the FGF-2 signaling pathway and its potential application as a supramolecular scaffold that can be used in vivo as an alternative to the encapsulation and delivery of the native FGF-2 protein.

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. In the stable crystalline phase, the molecules end up organized in a short scroll morphology at high ionic strengths and as long helical ribbons at lower salt content. This is interpreted as the result of the competition between electrostatic repulsive forces and attractive molecular interactions. Only the stable phase forms charge-transfer excitons upon exposure to visible light as indicated by absorbance and fluorescence features, second-order harmonic generation microscopy, and femtosecond transient absorbance spectroscopy. Interestingly, the supramolecular reconfiguration to the stable crystalline phase nanostructures enhances photosensitization of a proton reduction catalyst for hydrogen production.

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 31.6 µm thick polystyrene (PS) support film for eliminating the substrate contribution, (ii) an unfilled PS-b-P2VP micelle supported by the same PS film, and (iii) a ZnAc-loaded PS-b-P2VP micelle supported by the same PS film. Force-indentation (F-I) curves were measured over unloaded micelles on the PS film and over loaded micelles on the PS film, using standard tapping mode probes of three different spring constants, the same cantilevers used for imaging of the samples before and after loading. For calibration of the tip geometry, nanoindentation was performed on the bare PS film. The resulting elastic modulus values extracted by applying the Hertz model were 8.26 ± 3.43 GPa over the loaded micelles and 4.17 ± 1.65 GPa over the unloaded micelles, confirming that phase contrast images of a monolayer of loaded micelles represent maps of the nanoscale chemical and mechanical variation. By calibrating the tip geometry indirectly using a known soft material, we are able to use the same standard tapping mode cantilevers for both imaging and indentation.

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. Thermal annealing was found to increase power conversion efficiencies by promoting domain growth while still maintaining this percolating network of nanostructures. The benefits of self-assembly and grooved nanowires were examined by building devices from a soluble sexithiophene derivative that does not form one-dimensional structures. In these systems, excessive phase separation caused by thermal annealing leads to the formation of defects and lower device efficiencies. We propose that the unique hairpin shape of the self-assembling molecules allows the nanowires as they form to interact well with the fullerenes in receptor-ligand type configurations at the heterojunction of the two domains, thus enhancing device efficiencies by 23%.

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. Determining the chemical distribution with high nanoscale spatial resolution is shown to complement the less direct characterization by AFM, DLS and FTIR, thus demonstrating broader implications for the characterization of hybrid nanocomposite systems.

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. The broader implications are significant for scanning probe microscopy of other soft materials systems containing the segregation of a harder phase.