Unraveling intra-aggregate structural disorder using single-molecule spectroscopy.

Structural disorder within self-assembled molecular aggregates may have strong effects on their optical functionality. Such disorder, however, is hard to explore using standard ensemble measurements. In this paper, we report on the characterization of intra-aggregate structural disorder through a linewidth analysis of fluorescence excitation experiments on individual zinc-chlorin (ZnChl) nanotubular molecular aggregates. Recent experiments suggest an anomaly in the linewidths of the two absorption bands that dominate the spectra: the higher-energy bands on average show a smaller linewidth than the lower-energy bands. This anomaly is explored in this paper by analyzing and modeling the correlation of the two linewidths for each aggregate. We exploit a Frenkel exciton model to show that the experimentally observed correlation of linewidths and other statistical properties of the single-aggregate spectra can be explained from small variations of the molecular orientations within individual aggregates.

Spectral and Structural Variations of Biomimetic Light-Harvesting Nanotubes.

Bioinspired, self-assembled nanotubes have been investigated by low-temperature, polarization-resolved single-tube spectroscopy. These assemblies are based on zinc chlorin monomers and are considered as model systems that resemble the secondary structural elements in the natural light-harvesting systems of green (non)sulfur bacteria. Compared to the natural systems, the spectral parameters extracted from the single-nanotube spectra feature distributions with significantly smaller widths, which is ascribed to a tremendous reduction of structural heterogeneity in the artificial systems. Employing quantum chemical molecular modeling the spectra of individual nanotubes can be explained consistently only for a molecular packing model that is fundamentally different from those considered so far for the natural systems. Subsequent theoretical simulations reveal that the remaining spectral variations between single nanotubes can be traced back to small variations of the mutual orientations of the monomer transition dipole moments that are far beyond the resolving power of high-resolution electron microscopy imaging techniques.

The GURKE gene is required for normal organization of the apical region in the Arabidopsis embryo.

Dicot plant embryos undergo a transition from radial to bilateral symmetry. In Arabidopsis, this change reflects patterning within the apical region, resulting in the formation of the cotyledon and shoot meristem primordia. Mutations in the GURKE gene give seedlings with highly reduced or no cotyledons. Both strong and weak gurke alleles confer this phenotypic variability although strong alleles often eliminate the entire apex and sometimes also part of the hypocotyl. The root and the root meristem as well as the radial pattern of concentric tissue layers are essentially normal. The mutant seedling phenotype can be traced back to the triangular/early-heart stage of embryogenesis when abnormal cell divisions occur within the apical region such that no or only rudimentary cotyledon primordia are established. The postembryonic development of gurke seedlings was examined in culture. In weak alleles, apical growth gave rise to abnormal leaves and stem-like structures and, eventually, abnormal flowers. In strong alleles, the apical region often failed to grow but occasionally produced fused leaf-like structures with no dorso-ventral polarity and a totally unorganized vascular system while no stems developed. The observations suggest that the GURKE gene is involved primarily in the organization of the apical region in the embryo and may also play a role during postembryonic development.