Picosecond time-resolved photon antibunching measures nanoscale exciton motion and the true number of chromophores.

The particle-like nature of light becomes evident in the photon statistics of fluorescence from single quantum systems as photon antibunching. In multichromophoric systems, exciton diffusion and subsequent annihilation occurs. These processes also yield photon antibunching but cannot be interpreted reliably. Here we develop picosecond time-resolved antibunching to identify and decode such processes. We use this method to measure the true number of chromophores on well-defined multichromophoric DNA-origami structures, and precisely determine the distance-dependent rates of annihilation between excitons. Further, this allows us to measure exciton diffusion in mesoscopic H- and J-type conjugated-polymer aggregates. We distinguish between one-dimensional intra-chain and three-dimensional inter-chain exciton diffusion at different times after excitation and determine the disorder-dependent diffusion lengths. Our method provides a powerful lens through which excitons can be studied at the single-particle level, enabling the rational design of improved excitonic probes such as ultra-bright fluorescent nanoparticles and materials for optoelectronic devices.

Switching between H- and J-type electronic coupling in single conjugated polymer aggregates.

The aggregation of conjugated polymers and electronic coupling of chromophores play a central role in the fundamental understanding of light and charge generation processes. Here we report that the predominant coupling in isolated aggregates of conjugated polymers can be switched reversibly between H-type and J-type coupling by partially swelling and drying the aggregates. Aggregation is identified by shifts in photoluminescence energy, changes in vibronic peak ratio, and photoluminescence lifetime. This experiment unravels the internal electronic structure of the aggregate and highlights the importance of the drying process in the final spectroscopic properties. The electronic coupling after drying is tuned between H-type and J-type by changing the side chains of the conjugated polymer, but can also be entirely suppressed. The types of electronic coupling correlate with chain morphology, which is quantified by excitation polarization spectroscopy and the efficiency of interchromophoric energy transfer that is revealed by the degree of single-photon emission.

Impaired insulin secretion and glucose tolerance in beta cell-selective Ca(v)1.2 Ca2+ channel null mice.

Insulin is secreted from pancreatic beta cells in response to an elevation of cytoplasmic Ca(2+) resulting from enhanced Ca(2+) influx through voltage-gated Ca(2+) channels. Mouse beta cells express several types of Ca(2+) channel (L-, R- and possibly P/Q-type). beta cell-selective ablation of the gene encoding the L-type Ca(2+) channel subtype Ca(v)1.2 (betaCa(v)1.2(-/-) mouse) decreased the whole-cell Ca(2+) current by only approximately 45%, but almost abolished first-phase insulin secretion and resulted in systemic glucose intolerance. These effects did not correlate with any major effects on intracellular Ca(2+) handling and glucose-induced electrical activity. However, high-resolution capacitance measurements of exocytosis in single beta cells revealed that the loss of first-phase insulin secretion in the betaCa(v)1.2(-/-) mouse was associated with the disappearance of a rapid component of exocytosis reflecting fusion of secretory granules physically attached to the Ca(v)1.2 channel. Thus, the conduit of Ca(2+) entry determines the ability of the cation to elicit secretion.