On-Surface Synthesis of Cumulene-Containing Polymers via Two-Step Dehalogenative Homocoupling of Dibromomethylene-Functionalized Tribenzoazulene

Cumulene compounds are notoriously difficult to prepare and study because their reactivity increases dramatically with the increasing number of consecutive double bonds. In this respect, the emerging field of on-surface synthesis provides exceptional opportunities because it relies on reactions on clean metal substrates under well-controlled ultrahigh-vacuum conditions. Here we report the on-surface synthesis of a polymer linked by cumulene-like bonds on a Au(111) surface via sequential thermally activated dehalogenative C−C coupling of a tribenzoazulene precursor equipped with two dibromomethylene groups. The structure and electronic properties of the resulting polymer with cumulene-like pentagon–pentagon and heptagon–heptagon connections have been investigated by means of scanning probe microscopy and spectroscopy methods and X-ray photoelectron spectroscopy, complemented by density functional theory calculations. Our results provide perspectives for the on-surface synthesis of cumulene-containing compounds, as well as protocols relevant to the stepwise fabrication of carbon–carbon bonds on surfaces.     

Protein Allostery at Atomic Resolution

Protein allostery is a phenomenon involving the long range coupling between two distal sites in a protein. In order to elucidate allostery at atomic resoluion on the ligand-binding WW domain of the enzyme Pin1, multistate structures were calculated from exact nuclear Overhauser effect (eNOE). In its free form, the protein undergoes a microsecond exchange between two states, one of which is predisposed to interact with its parent catalytic domain. In presence of the positive allosteric ligand, the equilibrium between the two states is shifted towards domain–domain interaction, suggesting a population shift model. In contrast, the allostery-suppressing ligand decouples the side-chain arrangement at the inter-domain interface thereby reducing the inter-domain interaction. As such, this mechanism is an example of dynamic allostery. The presented distinct modes of action highlight the power of the interplay between dynamics and function in the biological activity of proteins.     

Collective All‐Carbon Magnetism in Triangulene Dimers

Triangular zigzag nanographenes, such as triangulene and its π‐extended homologues, have received widespread attention as organic nanomagnets for molecular spintronics, and may serve as building blocks for high‐spin networks with long‐range magnetic order, which are of immense fundamental and technological relevance. As a first step towards these lines, we present the on‐surface synthesis and a proof‐of‐principle experimental study of magnetism in covalently bonded triangulene dimers. On‐surface reactions of rationally designed precursor molecules on Au(111) lead to the selective formation of triangulene dimers in which the triangulene units are either directly connected through their minority sublattice atoms, or are separated via a 1,4‐phenylene spacer. The chemical structures of the dimers have been characterized by bond‐resolved scanning tunneling microscopy. Scanning tunneling spectroscopy and inelastic electron tunneling spectroscopy measurements reveal collective singlet–triplet spin excitations in the dimers, demonstrating efficient intertriangulene magnetic coupling.     

Reduction of Oxide Minerals by Hydrogen Plasma: An Overview

Carbothermic reduction of oxide minerals is one of the major routes to obtain the corresponding metals. This process produces a lot of CO₂, which is responsible for greenhouse effect. Alternatively, hydrogen plasma containing hydrogen in atomic, ionic, and excited states can reduce almost every metal oxide even at lower temperatures. Besides this advantage, plasma processing also offers kinetic advantages. Further, hydrogen-water cycle does not pose any environmental problems. However, reduction of metal oxides in hydrogen plasma is not so straightforward—there are issues relating to introduction of material into the plasma zone, residence time, reverse reaction, and scale-up that must be resolved—yet, it holds the key to future environmental challenges particularly with respect to CO₂ emission. This paper provides an overview of reduction of oxide minerals by hydrogen plasma. The influences of various reaction conditions particularly with respect to reduction of oxides are discussed and some aspects of both thermal and non-thermal cold plasma linking oxidative as well as dissociative reduction are presented.     

Diffraction of sound pulses by a rigid cylinder in an inhomogeneous medium

We consider the problem of scattering of two-dimensional sound pulses by a rigid circular cylinder embedded in a cylindrically stratified inhomogeneous medium. The line source is parallel to the axis of the cylinder. It is assumed that the velocity of soundc is given byc ^?1=pr ^q, wherep andq are real constants andp>0. The method of dual integral transformation developed by Friedlander is used. The solution in terms of pulse propagation modes gives the diffracted pulse and the method of steepest descents yields the geometrical acoustic field.     

Propagation of sound pulses in a semiinfinite stratified medium

We consider the propagation of sound pulses due to a line source in the inhomogeneous, semi-infinite mediumy ≥ 0 with the boundary conditionφ=0 or?φ/(?y)=0 aty=0, whereφ is the acoustic velocity potential. We suppose that the velocity of wave propagation,c, is given byc ^?2=p ?qe ^?ay , wherep, q, α are real and positive andp>q. The method of dual integral transformation is used. The solution in terms of pulse propagation modes yields the diffracted pulse and the method of steepest descents gives the geometrical acoustic field.