Large Enhancement of the Single-Molecular Conductance of a Molecular Wire through a Radical Substituent

The single-molecular conductance between two π-conjugated wires with and without a radical substituent has been compared. Specifically, methyl- and iminonitroxide-substituted 4-(biphenyl-4-yl)pyridine wires bound onto a porphyrin template were subjected to scanning tunneling microscopy (STM) apparent-height measurement at the interface between highly oriented pyrolytic graphite (HOPG) and octan-1-oic acid. Statistical analysis of the STM images revealed that the radical-substituted wire has 3.2±1.7-fold higher conductance than the methyl-substituted reference. Although density functional theory (DFT) calculation suggests that only 17 % of the SOMO is distributed on the wire moiety, the effect was significant. This study presents the potential of radical substituents to achieve high conductivity in molecular wires.     

Key Role of a-Top CO on Terrace Sites of Metallic Pd Clusters for CO Oxidation

Pd-based catalysts are the most widely used for CO oxidation because of their outstanding catalytic activity and thermal stability. However, fundamental understanding of the detailed catalytic processes occurring on Pd-based catalysts under realistic conditions is still lacking. In this study, we investigated CO oxidation on metallic Pd clusters supported on Al₂O₃ and SiO₂. High-angle annular dark-field scanning transmission electron microscopy revealed the formation of similar-sized Pd clusters on Al₂O₃ and SiO₂. In contrast, CO chemisorption analysis indicated a gradual change in the dispersion of Pd (from 0.79 to 0.2) on Pd/Al₂O₃ and a marginal change in the dispersion (from 0.4 to 0.24) on Pd/SiO₂ as the Pd loading increased from 0.27 to 5.5 wt %; these changes were attributed to differences in the metal-support interactions. Diffuse reflectance infrared Fourier-transform spectroscopy revealed that fewer a-top CO species were present in Pd supported on Al₂O₃ than those in Pd supported on SiO₂, which is related to the morphological differences in the metallic Pd clusters on these two supports. Despite the different dispersion profiles and surface characteristics of Pd, O₂ titration demonstrated that linearly bound CO (with an infrared signal at 2090 cm⁻¹) reacted first with oxygen in the case of CO-saturated Pd on Al₂O₃ and SiO₂, which suggests that a-top CO on the terrace site plays an important role in CO oxidation. The experimental observations were corroborated by periodic density functional calculations, which confirmed that CO oxidation on the (111) terrace sites is most plausible, both kinetically and thermodynamically, compared to that on the edge or corner sites. This study will deepen the fundamental understanding of the effect of Pd clusters on CO oxidation under reaction conditions.     

Effect of wall slip on the viscoelastic particle ordering in a microfluidic channel

The formation of a line of equally spaced particles at the centerline of a microchannel, referred as “particle ordering,” is desired in several microfluidic applications. Recent experiments and simulations highlighted the capability of viscoelastic fluids to form a row of particles characterized by a preferential spacing. When dealing with non-Newtonian fluids in microfluidics, the adherence condition of the liquid at the channel wall may be violated and the liquid can slip over the surface, possibly affecting the ordering efficiency. In this work, we investigate the effect of wall slip on the ordering of particles suspended in a viscoelastic liquid by numerical simulations. The dynamics of a triplet of particles in an infinite cylindrical channel is first addressed by solving the fluid and particle governing equations. The relative velocities computed for the three-particle system are used to predict the dynamics of a train of particles flowing in a long microchannel. The distributions of the interparticle spacing evaluated at different slip coefficients, linear particle concentrations, and distances from the channel inlet show that wall slip slows down the self-assembly mechanism. For strong slipping surfaces, no significant change of the initial microstructure is observed at low particle concentrations, whereas strings of particles in contact form at higher concentrations. The detrimental effect of wall slip on viscoelastic ordering suggests care when designing microdevices, especially in case of hydrophobic surfaces that may enhance the slipping phenomenon.     

有机张力半导体及其光电特性

分子张力作为空间设计的重要组成部分正成为调控有机半导体的重要手段。由于分子内产生的拉伸张力、扭曲/弯曲张力以及空间张力而导致p轨道排布重组和构型构象结构发生变化,最近各种几何与拓扑结构的高张力有机半导体材料相继被报道,这使得高张力有机半导体材料成为有机电子领域研究的焦点。为了进一步梳理分子张力在有机半导体材料中扮演的角色与价值,该综述从分子张力的类型、实验与理论量化以及可视化出发,总结了高张力共轭芳烃的分子设计策略、与其光电性能分子张力之间的关系,以及这类新兴材料在光电领域的应用。最后,对高张力共轭芳烃的研究前景进行了展望,阐述了该类材料所面临的机遇与挑战。     

Electro-assisted Molecular Assembly Giving Atomic-Scale Catalytic Active-Site Detection

The artificially accurate design of nonmetal electrocatalysts’ active site has been a huge challenge because no pure active species with the specific structure could be strictly controlled by traditional synthetic methods. Species with a multiconfiguration in the catalyst hinder identification of the active site and the subsequent comprehension of the reaction mechanism. We have developed a novel electro-assisted molecular assembly strategy to obtain a pure pentagon ring on perfect graphene avoiding other reconstructed structures. More importantly, the active atom was confirmed by the subtle passivation process as the topmost carbon atom. Recognition of the carbon-defect electrocatalysis reaction mechanism was first downsized to the single-atom scale from the experimental perspective. It is expected that this innovative electro-assisted molecular assembly strategy could be extensively applied in the active structure-controlled synthesis of nonmetal electrocatalysts and verification of the exact active atom.     

Conformational change-modulated spin transport at single-molecule level in carbon systems

Controlling the spin transport at the single-molecule level, especially without the use of ferromagnetic contacts, becomes a focus of research in spintronics. Inspired by the progress on atomic-level molecular synthesis, through first-principles calculations, we investigate the spin-dependent electronic transport of graphene nanoflakes with side-bonded functional groups, contacted by atomic carbon chain electrodes. It is found that, by rotating the functional group, the spin polarization of the transmission at the Fermi level could be switched between completely polarized and unpolarized states. Moreover, the transition between spin-up and spin-down polarized states can also be achieved, operating as a dual-spin filter. Further analysis shows that, it is the spin-dependent shift of density of states, caused by the rotation, that triggers the shift of transmission peaks, and then results in the variation of spin polarization. Such a feature is found to be robust to the length of the nanoflake and the electrode material, showing great application potential. Those findings may throw light on the development of spintronic devices.     

A nonlinear model for marble sulphation including surface rugosity and mechanical damage

Here we propose and analyze a mathematical model that aims to describe the marble sulphation process occurring in a given material. The model accounts for rugosity as well as for damaging effects. This model is characterized by some technical difficulties that seem hard to overcome from a theoretical viewpoint. Therefore, we introduce some physically reasonable modifications in order to establish the existence of a suitable notion of solution on a given time interval. Numerical simulations are presented and discussed, also in view of further research.     

Solid-state luminescence of Au(I) complexes with external stimuli-responsive properties

In the last decade, the field of stimuli-responsive luminescent materials have been intensely emerged because of the high potential application to functional sensors or photoelectronic devices. In particular, luminescent molecular crystals constructed from Au(I) complexes have produced a wide range of examples of luminescent alterations when some external stimulations, such as heat, mechanical stress, vapor (or solvents), were applied to the solid samples. In this review, we describe the recent progress through a summary of the reported Au(I) complexes based on their utilized stimuli-responsive mechanisms, which are categorized in crystal phase transitions (“crystal-to-amorphous”, “crystal-to-crystal” and “single-crystal-to-single-crystal” transitions) and molecular rotation in crystalline media, respectively.     

Mechanical property and deformation mechanism of gold nanowire with non-uniform distribution of twinned boundaries:A molecular dynamics simulation study

The mechanical property and deformation mechanism of twinned gold nanowire with non-uniform distribution of twinned boundaries(TBs) are studied by the molecular dynamics(MD) method. It is found that the twin boundary spacing(TBS) has a great effect on the strength and plasticity of the nanowires with uniform distribution of TBs. And the strength enhances with the decrease of TBS, while its plasticity declines. For the nanowires with non-uniform distribution of TBs, the differences in distribution among different TBSs have little effect on the Young's modulus or strength, and the compromise in strength appears. But the differences have a remarkable effect on the plasticity of twinned gold nanowire. The twinned gold nanowire with higher local symmetry ratio has better plasticity. The initial dislocations always form in the largest TBS and the fracture always appears at or near the twin boundaries adjacent to the smallest TBS. Some simulation results are consistent with the experimental results.     

A Molecular Cable Car for Transmembrane Ion Transport

The controlled transport of molecular and ionic substrates across bilayer membranes is a fundamental task for the operation of living organisms. It is also a highly fascinating and demanding challenge for artificial molecular machines. The recent report of a synthetic transmembrane molecular shuttle that can transport potassium ions selectively down a gradient in a liposomal system makes a small but significant step towards this goal.