Structure and Conductivity of Semiconducting Polymer Hydrogels.

Poly(fluorene-alt-thiophene) (PFT) is a conjugated polyelectrolyte that self-assembles into rod-like micelles in water, with the conjugated polymer backbone running along the length of the micelle. At modest concentrations (∼10 mg/mL in aqueous solutions), PFT forms hydrogels, and this work focuses on understanding the structure and intermolecular interactions in those gel networks. The network structure can be directly visualized using cryo electron microscopy. Oscillatory rheology studies further tell us about connectivity within the gel network, and the data are consistent with a picture where polymer chains bridge between micelles to hold the network together. Addition of tetrahydrofuran (THF) to the gels breaks those connections, but once the THF is removed, the gel becomes stronger than it was before, presumably due to the creation of a more interconnected nanoscale architecture. Small polymer oligomers can also passivate the bridging polymer chains, breaking connections between micelles and dramatically weakening the hydrogel network. Fits to solution-phase small-angle X-ray scattering data using a Dammin bead model support the hypothesis of a bridging connection between PFT micelles, even in dilute aqueous solutions. Finally, time-resolved microwave conductivity measurements on dried samples show an increase in carrier mobility after THF annealing of the PFT gel, likely due to increased connectivity within the polymer network.

Entropic chiral symmetry breaking in self-organized two-dimensional colloidal crystals.

Long-range chiral symmetry breaking (CSB) has been recently observed in 2D self-organized rhombic crystals of hard, achiral, 72 degree rhombic microparticles. However, purely entropic selection of a CSB crystal in an idealized system of hard achiral shapes, in which attractions are entirely absent and the shape does not dictate a chiral tiling, has not yet been quantitatively predicted. Overcoming limitations of a purely rotational cage model, we investigate a translational-rotational cage model (TRCM) of dense systems of hard achiral rhombs and quantitatively demonstrate that entropy can spontaneously drive the preferential self-organization of a chiral crystal composed of achiral shapes that also tile into an achiral crystal. At different particle area fractions, ϕA, we calculate the number of accessible translational-rotational microstates, Ω, of a mobile central rhomb in a static cage of neighboring rhombs, which can have different orientation angles, γ, relative to the bisector of the crystalline axes. As we raise ϕA, two maxima emerge in Ω(γ) at non-zero cage orientation angles, ±Î³max. These maxima correspond to additional translational microstates that become accessible in the CSB crystalline polymorph through reduced translational tip-tip interference. Thus, entropy, often associated with structural disorder, can drive CSB in condensed phase systems of non-attractive achiral objects that do not tile into chiral structures. The success of the TRCM in explaining the entropic origin of CSB in systems of hard rhombs indicates that the TRCM will have significant utility in predicting the self-organized behavior of dense systems of other hard shapes in 2D.

Rotational Fourier tracking of diffusing polygons.

We use optical microscopy to measure the rotational Brownian motion of polygonal platelets that are dispersed in a liquid and confined by depletion attractions near a wall. The depletion attraction inhibits out-of-plane translational and rotational Brownian fluctuations, thereby facilitating in-plane imaging and video analysis. By taking fast Fourier transforms (FFTs) of the images and analyzing the angular position of rays in the FFTs, we determine an isolated particle's rotational trajectory, independent of its position. The measured in-plane rotational diffusion coefficients are significantly smaller than estimates for the bulk; this difference is likely due to the close proximity of the particles to the wall arising from the depletion attraction.