A bulk material comprising stacked nanosheets of nickel bis(dithiolene) complexes is investigated. The average oxidation number is -3/4 for each complex unit in the as-prepared sample; oxidation or reduction respectively can change this to 0 or -1. Refined electrical conductivity measurement, involving a single microflake sample being subjected to the van der Pauw method under scanning electron microscopy control, reveals a conductivity of 1.6 × 10(2) S cm(-1), which is remarkably high for a coordination polymeric material. Conductivity is also noted to modulate with the change of oxidation state. Theoretical calculation and photoelectron emission spectroscopy reveal the stacked nanosheets to have a metallic nature. This work provides a foothold for the development of the first organic-based two-dimensional topological insulator, which will require the precise control of the oxidation state in the single-layer nickel bisdithiolene complex nanosheet (cf. Liu, F. et al. Nano Lett. 2013, 13, 2842).

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Amyloid fibrillation causes serious neurodegenerative diseases and amyloidosis; however, the detailed mechanisms by which the structural states of precursor proteins in a lipid membrane-associated environment contribute to amyloidogenesis still remains to be elucidated. We examined the relationship between structural states of intrinsically-disordered wild-type and mutant α-synuclein (αSN) and amyloidogenesis on two-types of model membranes. Highly-unstructured wild-type αSN (αSN) and a C-terminally-truncated mutant lacking negative charges (αSN) formed amyloid fibrils on both types of membranes, the model membrane mimicking presynaptic vesicles (Mimic membrane) and the model membrane of 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC membrane). Unstructured αSN and αSN both bound to Mimic membranes in a helical conformation with similar binding affinity. Promotion and then inhibition of amyloidogenesis of αSN were observed as the concentration of Mimic lipids increased. We explain this by the two-state binding model: at lower lipid concentrations, binding of αSN to membranes enhances amyloidogenicity by increasing the local concentration of membrane-bound αSN and so promoting amyloid nucleation; at higher lipid concentrations, membrane-bound αSN is actually in a sense diluted by increasing the number of model membranes, which blocks amyloid fibrillation due to an insufficient bound population for productive nucleation. Meanwhile, αSN formed amyloid fibrils over the whole concentration of Mimic lipids used here without inhibition, revealing the importance of helical structures for binding affinity and negatively charged unstructured C-terminal region for modulating amyloidogenesis. We propose that membrane binding-induced initial conformations of αSN, its overall charge states, and the population of membrane-bound αSN are key determinants of amyloidogenesis on membranes.

Graphdiyne (GDY), a two-dimensional allotrope of graphene, was first synthesized in 2010 and has attracted attention as a new low-dimensional carbon material. This work surveys the literature on GDYs. The history of GDYs is summarized, including their relationship with two-dimensional graphyne carbons and yearly publication trends. GDY is a molecule-based nanosheet woven from a molecular monomer, hexaethynylbenzene; thus, it is synthesized by bottom-up approaches, which allow rich variation via monomer design. The GDY family and the synthetic procedures are also described. Highly developed -conjugated electronic structures are common important features in GDY and graphene; however, the coexistence of sp and sp 2 carbons differentiates GDY from graphene. This difference gives rise to unique physical properties, such as high conductivity and large carrier mobility. Next, the theoretical and experimental studies of these properties are described in detail. A wide variety of applications have been proposed for GDYs, including electrocatalysts and energy devices, which exploit the carbon-rich nature, porous framework, and expanded -electron system of these compounds. Finally, potential uses are discussed.

We studied the atomic and electronic structures of ultrathin Bi(111) films grown on Bi(2)Te(3) by means of angle-resolved photoemission, first-principles calculations, and low-energy electron diffraction. These Bi films were found to be strained due to the influence of the substrate. Accordingly, the band structure is affected and Bi undergoes a topological phase transition; it is shown that the Z(2) topological invariant in three dimensions switches from +1 (trivial) to -1 (nontrivial or topological). This was clearly confirmed from the change in the surface-state dispersion near the Fermi level. Our discovery offers a method to produce novel topological systems from simple materials.