Engineering Synthetic Electron Transfer Chains from Metallopeptide Membranes.

The energetic and geometric features enabling redox chemistry across the copper cupredoxin fold contain key components of electron transfer chains (ETC), which have been extended here by templating the cross-ß bilayer assembly of a synthetic nonapeptide, HHQALVFFA-NH2 (K16A), with copper ions. Similar to ETC cupredoxin plastocyanin, these assemblies contain copper sites with blue-shifted (λmax 573 nm) electronic transitions and strongly oxidizing reduction potentials. Electron spin echo envelope modulation and X-ray absorption spectroscopies define square planar Cu(II) sites containing a single His ligand. Restrained molecular dynamics of the cross-ß peptide bilayer architecture support metal ion coordination stabilizing the leaflet interface and indicate that the relatively high reduction potential is not simply the result of distorted coordination geometry (entasis). Cyclic voltammetry (CV) supports a charge-hopping mechanism across multiple copper centers placed 10-12 Å apart within the assembled peptide leaflet interface. This metal-templated scaffold accordingly captures the electron shuttle and cupredoxin functionality in a peptide membrane-localized electron transport chain.

Physiology and whole-plant carbon partitioning during stem sugar accumulation in sweet dwarf sorghum.

MAIN CONCLUSION: A greater rate of phloem unloading and storage in the stem, not a higher rate of sugar production by photosynthesis or sugar export from leaves, is the main factor that results in sugar accumulation in sweet dwarf sorghum compared to grain sorghum. At maturity, the stem internodes of sweet sorghum varieties accumulate high concentrations of fermentable sugars and represent an efficient feedstock for bioethanol production. Although stem sugar accumulation is a heritable trait, additional factors that drive sugar accumulation in sorghum have not been identified. To identify the constraints on stem sugar accumulation in sweet sorghum, we used a combination of carbon-11 (11C) radiotracer, physiological and biochemical approaches, and compared a grain sorghum and sweet dwarf sorghum line that have similar growth characteristics including height. Photosynthesis did not increase during development or differ between the sorghum lines. During the developmental transition to the reproductive stage, export of 11C from leaves approximately doubled in both sorghum lines, but 11C export in the sweet dwarf line did not exceed that of the grain sorghum. Defoliation to manipulate relative sink demand did not result in increased photosynthetic rates, indicating that the combined accumulation of C by all sink tissues was limited by the maximum photosynthetic capacity of source leaves. Nearly 3/4 of the 11C exported from leaves was transported to the lower stem in sweet sorghum within 2 h, whereas in grain sorghum nearly 3/4 of the 11C was in the panicle. Accordingly, the transcripts of several sucrose transporter (SUT) genes were more abundant in the stem internodes of the sweet dwarf line compared to the grain sorghum. Overall, these results indicate that sugar accumulation in sweet sorghum stems is influenced by the interplay of different sink tissues for the same sugars, but is likely driven by elevated sugar phloem unloading and uptake capacity in mature stem internodes.

Amyloid scaffolds as alternative chlorosomes.

Living systems contain remarkable functional capability built within sophisticated self-organizing frameworks. Defining the assembly codes that coordinate these systems could greatly extend nanobiotechnology. To that end, we have highlighted the self-assembling architecture of the chlorosome antenna arrays and report the emulation and extension of their features for the development of cell-compatible photoredox materials. We specifically review work on amyloid peptide scaffolds able to (1) organize light-harvesting chromophores, (2) break peptide bilayer symmetry for directional energy and electron transfer, and (3) incorporate redox active metal ions at high density for energy storage.