Tuning conformation and properties of peptidomimetic backbones through dual N/Cα-substitution.

We demonstrate that changing the backbone between peptides, peptoids and the underexplored dual N/Cα-substituted peptoids analogues allows for control over the preferred conformation of the intrinsically disordered biomimetic oligomers. The conformation tunability is directly probed using electron paramagnetic resonance (EPR), and is shown to manifest itself in differences in the nanoparticle-oligomer hybridization propensity.

Catechol-based layer-by-layer assembly of composite coatings: a versatile platform to hierarchical nano-materials.

Inspired by the marine mussel's ability to adhere to surfaces underwater, an aqueous catechol-based dip coating platform was developed. Using a catechol-functionalized polyacrylamide binder in combination with inorganic nanoparticles enables the facile fabrication of robust composite coatings via a layer-by-layer process. This modular assembly of well-defined building blocks provides a versatile alternative to electrostatic driven approaches with layer thickness and refractive indices being readily tunable. The platform nature of this approach enables the fabrication of hierarchically ordered nano-materials such as Bragg stacks.

Determination of the electron escape depth for NEXAFS spectroscopy.

A novel method was developed to determine carbon atom density as a function of depth by analyzing the postedge signal in near-edge X-ray absorption fine structure (NEXAFS) spectra. We show that the common assumption in the analysis of NEXAFS data from polymer films, namely, that the carbon atom density is constant as a function of depth, is not valid. This analysis method is then used to calculate the electron escape depth (EED) for NEXAFS in a model bilayer system that contains a perfluorinated polyether (PFPE) on top of a highly oriented pyrolitic graphite (HOPG) sample. Because the carbon atom densitites of both layers are known, in addition to the PFPE surface layer thickness, the EED is determined to be 1.95 nm. This EED is then used to measure the thickness of the perfluorinated surface layer of poly(4-(1H,1H,2H,2H-perfluorodecyl)oxymethylstyrene) (PFPS).

Influence of molecular architecture on the dewetting of thin polystyrene films.

The control of dewetting for thin polymer films is a technical challenge and of significant academic interest. We have used polystyrene nanoparticles to inhibit dewetting of high molecular weight, linear polystyrene, demonstrating that molecular architecture has a unique effect on surface properties. Neutron reflectivity measurements were used to demonstrate that the nanoparticles were uniformly distributed in the thin (ca. 40 nm) film prior to high temperature annealing, yet after annealing, they were found to separate to the solid substrate, a silanized silicon wafer. Dewetting was eliminated when the nanoparticles separated to form a monolayer or above while below this surface coverage the dewetting dynamics was severely retarded. Blending linear polystyrene of similar molecular weight to the polystyrene nanoparticle with the high molecular weight polystyrene did not eliminate dewetting.

Self-encapsulation of poly-2,7-fluorenes in a dendrimer matrix.

The synthesis and characterization of complex dendritic, rigid rod poly-2,7-fluorene homopolymers and copolymers via a macromonomer approach is reported. Several 2,7-dibromofluorene monomers containing benzyl ether dendrons (generations 1, 2, and 3) in the 9,9'-position of the fluorene ring were prepared and employed in condensation polymerizations to yield both homopolymers and copolymers with diethylhexylfluorene. Fluorescence measurements of the materials reveal extensive conjugation along the polymer backbone. The determination of the solid-state PL spectra and quantum efficiencies showed that there is an apparent optimum size of the dendritic side groups with the [G-2]-derivatives showing high reactivity with associated site isolation of the conjugated chain. AFM analysis and DSC results confirmed that the hybrid polymers and copolymers did not show any sign of a microphase-separated morphology. First EL-results demonstrated that the homopolymers have higher turn-on voltages then the corresponding copolymers.

Adaptation of bulk constitutive equations to insoluble monolayer collapse at the air-water interface.

A constitutive equation based on stress-strain models of bulk solids was adapted to relate the surface pressure, compression rate, and temperature of an insoluble monolayer of monodendrons during collapse at the air-water interface. A power law relation between compression rate and surface pressure and an Arrhenius temperature dependence of the steady-state creep rate were observed in data from compression rate and creep experiments in the collapse region. These relations were combined into a single constitutive equation to calculate the temperature dependence of the collapse pressure with a maximum error of 5 percent for temperatures ranging from 10 degrees to 25 degrees C.