The Conductance of Porphyrin-Based Molecular Nanowires Increases with Length.

High electrical conductance molecular nanowires are highly desirable components for future molecular-scale circuitry, but typically molecular wires act as tunnel barriers and their conductance decays exponentially with length. Here, we demonstrate that the conductance of fused-oligo-porphyrin nanowires can be either length independent or increase with length at room temperature. We show that this negative attenuation is an intrinsic property of fused-oligo-porphyrin nanowires, but its manifestation depends on the electrode material or anchor groups. This highly desirable, nonclassical behavior signals the quantum nature of transport through such wires. It arises because with increasing length the tendency for electrical conductance to decay is compensated by a decrease in their highest occupied molecular orbital-lowest unoccupied molecular orbital gap. Our study reveals the potential of these molecular wires as interconnects in future molecular-scale circuitry.

Hemilabile Ligands as Mechanosensitive Electrode Contacts for Molecular Electronics.

Single-molecule junctions that are sensitive to compression or elongation are an emerging class of nanoelectromechanical systems (NEMS). Although the molecule-electrode interface can be engineered to impart such functionality, most studies to date rely on poorly defined interactions. We focused on this issue by synthesizing molecular wires designed to have chemically defined hemilabile contacts based on (methylthio)thiophene moieties. We measured their conductance as a function of junction size and observed conductance changes of up to two orders of magnitude as junctions were compressed and stretched. Localised interactions between weakly coordinating thienyl sulfurs and the electrodes are responsible for the observed effect and allow reversible monodentate⇄bidentate contact transitions as the junction is modulated in size. We observed an up to ≈100-fold sensitivity boost of the (methylthio)thiophene-terminated molecular wire compared with its non-hemilabile (methylthio)benzene counterpart and demonstrate a previously unexplored application of hemilabile ligands to molecular electronics.

Turning the Tap: Conformational Control of Quantum Interference to Modulate Single-Molecule Conductance.

Together with the more intuitive and commonly recognized conductance mechanisms of charge-hopping and tunneling, quantum-interference (QI) phenomena have been identified as important factors affecting charge transport through molecules. Consequently, establishing simple and flexible molecular-design strategies to understand, control, and exploit QI in molecular junctions poses an exciting challenge. Here we demonstrate that destructive quantum interference (DQI) in meta-substituted phenylene ethylene-type oligomers (m-OPE) can be tuned by changing the position and conformation of methoxy (OMe) substituents at the central phenylene ring. These substituents play the role of molecular-scale taps, which can be switched on or off to control the current flow through a molecule. Our experimental results conclusively verify recently postulated magic-ratio and orbital-product rules, and highlight a novel chemical design strategy for tuning and gating DQI features to create single-molecule devices with desirable electronic functions.

Adsorption of NO x (x = 1, 2) Molecules on the CoFeMnSi(001) Surface: First-Principles Insights.

In this article, the adsorption of NO x (x = 1, 2) gas molecules on the (001) surface of CoFeMnSi quaternary Heusler alloys has been investigated theoretically with density functional theory (DFT) calculations. The adsorption strength was estimated with adsorption energy (E a), magnitude of charge transfer (ΔQ), charge density difference (CDD), minimum distance between molecule and surface (d), and adsorption mechanism was analyzed with density of states. The results showed that unlike half-metallic nature of the bulk phase, the pristine CoFeMnSi(001) surface exhibited metallic character caused by the emergence of electronic states of the atoms in the top-most layer of the surface. It was found that both NO and NO2 molecules undergo chemical adsorption and strongly interact with the surface evidenced by the large value of E a and ΔQ. In particular, the NO x molecule dissociates into N and O atoms for some adsorption configurations. Bader charge analysis reveals that NO x molecules act as charge acceptors by drawing charge from the surface atoms through p-d hybridization. Such findings might be useful in the development of Heusler alloys based gas sensors.

Nasal Dermoid Cyst: A Case Report.

A dermoid cyst (DC) is a rare, benign congenital skin lesion that can occur anywhere on the skin and take any shape. DC is clinically diagnosed through imaging and biopsy. The usual treatment of choice for DC is surgical excision to prevent any local complications, such as inflammation, infection, and bone resorption. The type of surgery depends on the size, location, and extension of the cyst. When the cyst presents in certain areas, such as the nose, face, and scalp, surgery can be difficult owing to the possibility of an intracranial connection. Therefore, imaging is usually performed before intervening surgically. Here, we present the case of a two-year-old boy with no medical or surgical history who presented to our dermatology clinic with a slow-growing mass on his nose. During the consultation, the mass was examined, a complete medical history was obtained, and the patient was advised to undergo imaging, which revealed that the mass was a DC. Nevertheless, no deep connection was observed on imaging, and the mass was surgically removed without any complications.