Gel Trapping Enables Optical Spectroscopy of Single Solvated Conjugated Polymers in Equilibrium.

Single-molecule studies have provided a wealth of insight into the photophysics of conjugated polymers in the solid and desolvated state. Desolvating conjugated chains, e.g., by their embedding in inert solid matrices, invariably leads to chain collapse and the formation of intermolecular aggregates, which have a pronounced effect on their properties. By contrast, the luminescent properties of individual semiconducting polymers in their solvated and thermodynamic state remain largely unexplored. In this paper, we demonstrate a versatile gel trapping technique that enables the chemistry-free immobilization and interrogation of individual conjugated macromolecules, which retain a fully equilibrated conformation by contrast to conventional solid-state immobilization methods. We show how the technique can be used to record full luminescence spectra of single chains, to evaluate their time-resolved fluorescence, and to probe their photodynamics. Finally, we explore how the photophysics of different conjugated polymers is strongly affected by desolvation and chain collapse.

Rigidochromic conjugated polymers carrying main-chain molecular rotors.

We design and prepare rigidochromic conjugated polymers that carry molecular rotors in the main chain. We show how a suitable design maintains the mechanosensitivity of the rotors upon incorporation into an extended π-conjugated system. Construction of donor-acceptor polymers enables their use as ratiometric probes for polymer micromechanics, which we evidence through micromechanical imaging of a phase-separated polymer blend.

Two-dimensional crystals of star polymers: a tale of tails.

The formation of non-hexagonal crystalline structures by the organisation of colloidal nanoparticles often involves the use of complex particles with anisotropic shape or interactions or the imposition of non-uniform external fields. Here we explore how unusual symmetries can be created using experimentally realistic particles that interact through isotropic and purely repulsive potentials. In particular, we use simulations to explore the phase behavior of two-dimensional systems of star polymers. We uncover how the tail of the pair potential has a large role in dictating the phase behavior. Star polymers interacting in the far field with a Gaussian potential only form hexagonal phases, while an exponential tail gives rise to stable primitive oblique and honeycomb lattices. We identify the ratio in strength between long and short range interactions and the nature of the transition between these regimes as crucial parameters to predict when non-hexagonal crystals of star polymers can be stable. This leads to experimental design rules for creating star polymers which should exhibit unusual lattice formation.

Fragility and Strength in Nanoparticle Glasses.

Glasses formed from nano- and microparticles form a fascinating testing ground to explore and understand the origins of vitrification. For atomic and molecular glasses, a wide range of fragilities have been observed; in colloidal systems, these effects can be emulated by adjusting the particle softness. The colloidal glass transition can range from a superexponential, fragile increase in viscosity with increasing density for hard spheres to a strong, Arrhenius-like transition for compressible particles. However, the microscopic origin of fragility and strength remains elusive, both in the colloidal and in the atomic domains. Here, we propose a simple model that explains fragility changes in colloidal glasses by describing the volume regulation of compressible colloids in order to maintain osmotic equilibrium. Our simple model provides a microscopic explanation for fragility, and we show that it can describe experimental data for a variety of soft colloidal systems, ranging from microgels to star polymers and proteins. Our results highlight that the elastic energy per particle acts as an effective fragility order parameter, leading to a universal description of the colloidal glass transition.