Conductance Growth of Single-Cluster Junctions with Increasing Sizes.

Quantum-tunneling-based nanoelectronics has the potential for the miniaturization of electronics toward the sub-5 nm scale. However, the nature of phase-coherent quantum tunneling leads to the rapid decays of the electrical conductance with tunneling transport distance, especially in organic molecule-based nanodevices. In this work, we investigated the conductance of the single-cluster junctions of a series of atomically well-defined silver nanoclusters, with varying sizes from 0.9 to 3.0 nm, using the mechanically controllable break junction (MCBJ) technique combined with quantum transport theory. Our charge transport investigations of these single-cluster junctions revealed that the conductance grows with increasing cluster size. The conductance decay constant was determined to be ∼-0.4 nm-1, which is of opposite sign to that of organic molecules. Comparison between experiment and theory reveals that although charge transport through the silver single-cluster junctions occurs via phase-coherent tunneling, this is compensated by a rapid decrease in the energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital (HOMO-LUMO gap) with size and the increase in the electrode-cluster coupling, which results in their conductance increase up to lengths of ∼3.0 nm. These results demonstrate that such families of nanoclusters provide unique bottom-up building blocks for the fabrication of nanodevices in the sub-5 nm size range.

Tracking Confined Reaction Based on Host-Guest Interaction Using Single-Molecule Conductance Measurement.

The host-guest interaction acts as an essential part of supramolecular chemistry, which can be applied in confined reaction. However, it is challenging to obtain the dynamic process during confined reactions below micromolar concentrations. In this work, a new method is provided to characterize the dimerization process of the guest 1,2-bis(4-pyridinyl) ethylene in host cucurbit[8]curil using scanning tunneling microscope-break junction (STM-BJ) technique. The guest reaction kinetics is quantitatively by nuclear magnetic resonance (NMR) and in situ single-molecule junctions. It is found that in the single-molecule conductance measurements, the electrical signals of the reactants with a concentration as low as 5 × 10-6  m are clearly detected, and the reaction kinetics at micromolar concentrations are further obtained. However, in NMR measurements, the characteristic peak signal of the reactants is undetectable when the concentration of the reactants is lower than 0.5 × 10-3  m and it cannot be quantified. In addition, the strong electric field from the nanogap accelerates the reaction. This work reveals that single-molecule STM-BJ techniques are more sensitive for tracking confined reactions than that by NMR techniques and can be used to study effect of extremely strong electric field on kinetics.

Selective Fabrication of Single-Molecule Junctions by Interface Engineering.

Recent progress in addressing electrically driven single-molecule behaviors has opened up a path toward the controllable fabrication of molecular devices. Herein, the selective fabrication of single-molecule junctions is achieved by employing the external electric field. For molecular junctions with methylthio (-SMe), thioacetate (-SAc), amine (-NH2 ), and pyridyl (-PY), the evolution of their formation probabilities along with the electric field is extracted from the plateau analysis of individual single-molecule break junction traces. With the increase of the electric field, the SMe-anchored molecules show a different trend in the formation probability compared to the other molecular junctions, which is consistent with the density functional theory calculations. Furthermore, switching from an SMe-anchored junction to an SAc-anchored junction is realized by altering the electric field in a mixed solution. The results in this work provide a new approach to the controllable fabrication and modulation of single-molecule junctions and other bottom-up nanodevices at molecular scales.

Base-promoted regiodivergent allylation of N-acylhydrazones with Morita-Baylis-Hillman carbonates by tuning the catalyst.

A regiodivergent allylation of N-acylhydrazones with Morita-Baylis-Hillman (MBH) carbonates has been developed, providing α- or γ-allylated products in excellent yields by using different catalysts. The nature of the base catalyst plays a pivotal role in controlling the reaction pathway, allowing regiospecific access to diverse allylic substituted target compounds from identical substrates.

SOD3 suppresses early cellular immune responses to parasite infection.

Host immune responses are tightly controlled by various immune factors during infection, and protozoan parasites also manipulate the immune system to evade surveillance, leading to an evolutionary arms race in host‒pathogen interactions; however, the underlying mechanisms are not fully understood. We observed that the level of superoxide dismutase 3 (SOD3) was significantly elevated in both Plasmodium falciparum malaria patients and mice infected with four parasite species. SOD3-deficient mice had a substantially longer survival time and lower parasitemia than control mice after infection, whereas SOD3-overexpressing mice were much more vulnerable to parasite infection. We revealed that SOD3, secreted from activated neutrophils, bound to T cells, suppressed the interleukin-2 expression and concomitant interferon-gamma responses crucial for parasite clearance. Overall, our findings expose active fronts in the arms race between the parasites and host immune system and provide insights into the roles of SOD3 in shaping host innate immune responses to parasite infection.

A van der Waals heterojunction strategy to fabricate layer-by-layer single-molecule switch.

Single-molecule electronics offer a unique strategy for the miniaturization of electronic devices. However, the existing experiments are limited to the conventional molecular junctions, where a molecule anchors to the electrode pair with linkers. With such a rod-like configuration, the minimum size of the device is defined by the length of the molecule. Here, by incorporating a single molecule with two single-layer graphene electrodes, we fabricated layer-by-layer single-molecule heterojunctions called single-molecule two-dimensional van der Waals heterojunctions (M-2D-vdWHs), of which the sizes are defined by the thickness of the molecule. We controlled the conformation of the M-2D-vdWHs and the cross-plane charge transport through them with the applied electric field and established that they can serve as reversible switches. Our results demonstrate that the M-2D-vdWHs, as stacked from single-layer 2D materials and a single molecule, can respond to electric field stimulus, which promises a diverse class of single-molecule devices with unprecedented size.

σ-σ Stacked supramolecular junctions.

Intermolecular charge transport plays an essential role in organic electronic materials and biological systems. To date, experimental investigations of intermolecular charge transport in molecular materials and electronic devices have been restricted to conjugated systems in which π-π stacking interactions are involved. Herein we demonstrate that the σ-σ stacking interactions between neighbouring non-conjugated molecules offer an efficient pathway for charge transport through supramolecular junctions. The conductance of σ-σ stacked molecular junctions formed between two non-conjugated cyclohexanethiol or single-anchored adamantane molecules is comparable to that of π-π stacked molecular junctions formed between π-conjugated benzene rings. The current-voltage characteristics and flicker noise analysis demonstrate the existence of stacked molecular junctions formed between the electrode pairs and exhibit the characteristics of through-space charge transport. Density functional theory calculations combined with the non-equilibrium Green's function method reveal that efficient charge transport occurs between two molecules configured with σ-σ stacking interactions.

Facile Synthesis of Silver Nanoparticles with High Antibacterial Activity.

We report on a reverse microemulsion method for the synthesis of silver nanocrystals and examine their antibacterial activities. As the molar ratio of water to sodium bis(2-ethylhexyl) sulfosuccinate (AOT) increases to 25, a morphology transition from a sphere-like nanocrystal to a wire-like one was observed. For both the gram-negative and gram-positive bacteria, the wire-like silver nanocrystal showed higher antibacterial activities. We conclude that the morphology of silver nanocrystals dominates their antibacterial activity.

One-Pot Synthesis of Hierarchical Flower-Like Pd-Cu Alloy Support on Graphene Towards Ethanol Oxidation.

The synergetic effect of alloy and morphology of nanocatalysts play critical roles towards ethanol electrooxidation. In this work, we developed a novel electrocatalyst fabricated by one-pot synthesis of hierarchical flower-like palladium (Pd)-copper (Cu) alloy nanocatalysts supported on reduced graphene oxide (Pd-Cu(F)/RGO) for direct ethanol fuel cells. The structures of the catalysts were characterized by using scanning electron microscopy (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectrometer (XPS). The as-synthesized Pd-Cu(F)/RGO nanocatalyst was found to exhibit higher electrocatalytic performances towards ethanol electrooxidation reaction in alkaline medium in contrast with RGO-supported Pd nanocatalyst and commercial Pd black catalyst in alkaline electrolyte, which could be attributed to the formation of alloy and the morphology of nanoparticles. The high performance of nanocatalyst reveals the great potential of the structure design of the supporting materials for the future fabrication of nanocatalysts.