The role of interfacial donor-acceptor percolation in efficient and stable all-polymer solar cells.

Polymerization of Y6-type acceptor molecules leads to bulk-heterojunction organic solar cells with both high power-conversion efficiency and device stability, but the underlying mechanism remains unclear. Here we show that the exciton recombination dynamics of polymerized Y6-type acceptors (Y6-PAs) strongly depends on the degree of aggregation. While the fast exciton recombination rate in aggregated Y6-PA competes with electron-hole separation at the donor-acceptor (D-A) interface, the much-suppressed exciton recombination rate in dispersed Y6-PA is sufficient to allow efficient free charge generation. Indeed, our experimental results and theoretical simulations reveal that Y6-PAs have larger miscibility with the donor polymer than Y6-type small molecular acceptors, leading to D-A percolation that effectively prevents the formation of Y6-PA aggregates at the interface. Besides enabling high charge generation efficiency, the interfacial D-A percolation also improves the thermodynamic stability of the blend morphology, as evident by the reduced device "burn-in" loss upon solar illumination.

The effect of hydration and dehydration on the conformation, assembling behavior and photoluminescence of PBLG.

Hydration and dehydration play crucial roles in hydrophobic effects (HEs) and are yet to be understood. Poly(γ-benzyl-L-glutamate) (PBLG) homopolymers in THF/water with various water contents were investigated. We discovered that PBLG was hydrated at low water contents and adopted a helical conformation. The chain became dehydrated with increasing water content, which converted the PBLG100 helix to a PPII-helix. The variation in the conformation resulted in an alteration of the self-assembled morphologies from fibers to particles. For PBLG12 with a shorter chain, the chain underwent an α-to-ß transition in the conformation due to dehydration as the water content increased, and correspondingly the morphologies varied from tapes to helical ribbons, and eventually to toroids at a higher water content. We also observed that this α-to-ß transition is accompanied by an increase in intensity of the fluorescence, which is attributed to the through-space-conjugation of tightly packed phenyl groups within the ß-sheet. The discovered effect of hydration and dehydration on the PBLG chain conformation, self-assembling behavior and optical function is essential for the innovation of polypeptide materials and understanding of water-mediated biological systems.

Regulating the morphology and size of homopolypeptide self-assemblies via selective solvents.

It remains a great challenge to control the morphology and size of self-assembled homopolypeptide aggregates. In this work, rod-like micelles including spindles and cylinders were prepared by a solution self-assembly of poly(γ-benzyl-l-glutamate) (PBLG) homopolypeptides with different degrees of polymerization, in which their size was controlled precisely by tuning the ratio of water/methanol in selective cosolvents. The length of the rod-like micelles increased with an increasing amount of methanol in the selective cosolvents, which was confirmed using the combination of SEM, TEM and AFM. The self-assembly mechanism of PBLG in selective cosolvents was investigated by using complementary Fourier transform infrared (FT-IR), circular dichroism (CD) and low-field NMR analyses. It was found that the shrinkage and swelling of PBLG chains play important roles in the self-assembly process. The obtained results may provide a guideline for the study of regulating the assembled aggregate sizes.

Permo-Triassic boundary carbon and mercury cycling linked to terrestrial ecosystem collapse.

Records suggest that the Permo-Triassic mass extinction (PTME) involved one of the most severe terrestrial ecosystem collapses of the Phanerozoic. However, it has proved difficult to constrain the extent of the primary productivity loss on land, hindering our understanding of the effects on global biogeochemistry. We build a new biogeochemical model that couples the global Hg and C cycles to evaluate the distinct terrestrial contribution to atmosphere-ocean biogeochemistry separated from coeval volcanic fluxes. We show that the large short-lived Hg spike, and nadirs in δ202Hg and δ13C values at the marine PTME are best explained by a sudden, massive pulse of terrestrial biomass oxidation, while volcanism remains an adequate explanation for the longer-term geochemical changes. Our modelling shows that a massive collapse of terrestrial ecosystems linked to volcanism-driven environmental change triggered significant biogeochemical changes, and cascaded organic matter, nutrients, Hg and other organically-bound species into the marine system.