Self-Optimization of the Active Site of Molybdenum Disulfide by an Irreversible Phase Transition during Photocatalytic Hydrogen Evolution

The metallic 1T-MoS₂ has attracted considerable attention as an effective catalyst for hydrogen evolution reactions (HERs). However, the fundamental mechanism about the catalytic activity of 1T-MoS₂ and the associated phase evolution remain elusive and controversial. Herein, we prepared the most stable 1T-MoS₂ by hydrothermal exfoliation of MoS₂ nanosheets vertically rooted into rigid one-dimensional TiO₂ nanofibers. The 1T-MoS₂ can keep highly stable over one year, presenting an ideal model system for investigating the HER catalytic activities as a function of the phase evolution. Both experimental studies and theoretical calculations suggest that 1T phase can be irreversibly transformed into a more active 1T′ phase as true active sites in photocatalytic HERs, resulting in a “catalytic site self-optimization”. Hydrogen atom adsorption is the major driving force for this phase transition.     

Liquid-phase epitaxy of multicomponent layer-based porous coordination polymer thin films of [M(L)(P)0.5] type: importance of deposition sequence on the oriented growth

The progressive liquid-phase layer-by-layer (LbL) growth of anisotropic multicomponent layer-based porous coordination polymers (PCPs) of the general formula [M(L)(P)(0.5)] (M: Cu(2+), Zn(2+); L: dicarboxylate linker; P: dinitrogen pillar ligand) was investigated by using either pyridyl- or carboxyl-terminated self-assembled monolayers (SAMs) on gold substrates as templates. It was found that the deposition of smooth, highly crystalline, and oriented multilayer films of these PCPs depends on the conditions at the early growth cycles. In the case of a two-step process with an equimolar mixture of L and P, growth along the [001] direction is strongly preferred. However, employing a three-step scheme with full separation of all components allows deposition along the [100] direction on carboxyl-terminated SAMs. Interestingly, the growth of additional layers on top of previously grown oriented seeding layers proved to be insensitive to the particular growth scheme and full retention of the initial orientation, either along the [001] or [100] direction, was observed. This homo- and heteroepitaxial LbL growth allows full control over the orientation and the layer sequence, including introduction of functionalized linkers and pillars.     

Graphene: materials in the Flatland (Nobel lecture)

Much like the world described in Abbott's "Flatland", graphene is a two-dimensional object. And, as "Flatland" is "A Romance of Many Dimensions", graphene is much more than just a flat crystal. It possesses a number of unusual properties which are often unique or superior to those in other materials. In this brief lecture I would like to explain the reason for my (and many other people's) fascination with this material, and invite the reader to share some of the excitement I've experienced while researching it.     

Self-organisation of di(perfluorohexyl)hexane in Langmuir and LB films

Symmetrical triblock semifluorinated n-alkane, di(perfluorohexyl)hexane of the formula F(CF₂)₆(CH₂)₆(CF₂)₆F (abbreviated F₆H₆F₆), has been synthesised and investigated at the air/water interface. Our results show for the first time that this unusual film-forming material, completely hydrophobic in nature and possessing no polar group, is capable of stable film formation at the free water surface. The surface pressure–area isotherm of the studied compound exhibited two regions: corresponding to monotonous pressure rise, followed by a pseudo-plateau region. Visualisation of film structure with Brewster angle microscope (BAM) proved the formation of domains within the pseudo-plateau region. A closer insight into the structure of these domains with atomic force microscope (AFM) proved their ordered, circular shape. The average area of F₆H₆F₆ domain was found to depend on surface pressure value, as it is 4.98 ± 1.75 μm² at π = 1.2 mN/m to 16.54 ± 0.31 μm² at π = 1.7 mN/m. Following performed quantum-chemical calculations, it can be concluded that the observed surface aggregates from F₆H₆F₆ are formed by linear conformers with shifted CF and CH parts. The calculated domain thickness is between 20 and 21 Å, which perfectly agrees with the experimental value estimated from AFM measurements (20.3 ± 1.4 Å).     

Cannabidiol as Self-Assembly Inducer for Anticancer Drug-Based Nanoparticles

Cannabidiol (CBD) is a biologically active compound present in the plants of the Cannabis family, used as anticonvulsant, anti-inflammatory, anti-anxiety, and more recently, anticancer drug. In this work, its use as a new self-assembly inducer in the formation of nanoparticles is validated. The target conjugates are characterized by the presence of different anticancer drugs (namely N-desacetyl thiocolchicine, podophyllotoxin, and paclitaxel) connected to CBD through a linker able to improve drug release. These nanoparticles are formed via solvent displacement method, resulting in monodisperse and stable structures having hydrodynamic diameters ranging from 160 to 400 nm. Their biological activity is evaluated on three human tumor cell lines (MSTO-211H, HT-29, and HepG2), obtaining GI₅₀ values in the low micromolar range. Further biological assays were carried out on MSTO-211H cells for the most effective NP 8B, confirming the involvement of paclitaxel in cytotoxicity and cell death mechanism     

新奇半导体低维结构的自组织生长

文章介绍了自组织生长半导体量子线、量子点和量子环的进展,同时介绍了这些低维半导体材料在光电子和通信等领域应用情况.此外,对这些材料的一些测试方法也进行了介绍.     

Elucidating the Influence of Electrical Potentials on the Formation of Charged Oligopeptide Self-Assembled Monolayers on Gold

Self-assembled monolayers (SAMs) based on oligopeptides have garnered immense interest for a wide variety of innovative biomedical and electronic applications. However, to exploit their full potential, it is necessary to understand and control the surface chemistry of oligopeptides. Herein, we report on how different electrical potentials affect the adsorption kinetics, stability and surface coverage of charged oligopeptide SAMs on gold surfaces. Kinetic analysis using electrochemical surface plasmon resonance (e-SPR) reveals a slower oligopeptide adsorption rate at more positive or negative electrical potentials. Additional analysis of the potential-assisted formed SAMs by X-ray photoelectron spectroscopy demonstrates that an applied electrical potential has minimal effect on the packing density. These findings not only reveal that charged oligopeptides exhibit a distinct potential-assisted assembly behaviour but that an electrical potential offers another degree of freedom in controlling their adsorption rate.     

Self-Assembled CuCo2S4 Nanoparticles for Efficient Chemo-Photothermal Therapy of Arterial Inflammation

Cardiovascular disease caused by atherosclerosis (AS) seriously affects human health. Photothermal therapy (PTT) brings hope to the diagnosis and treatment of AS, with the development of nanotechnology. To improve treatment efficiency, self-assembled CuCo₂S₄ nanocrystals (NCs) were developed as a drug-delivery nanocarrier, triggered by near-infrared (NIR) light for efficient chemophotothermal therapy of arterial inflammation. The as-prepared self-assembled CuCo₂S₄ NCs exhibited excellent biocompatibility and a very high chloroquine (CL)-loading content. In addition, the self-assembled CuCo₂S₄ NCs/CL nanocomposites showed good photothermal performance, due to strong absorption in the NIR region, and the release of CL from the NCs/CL nanocomposites was driven by NIR light. When illuminated by NIR light, both PTT from the NCs and chemotherapy from the CL were simultaneously triggered, resulting in killing macrophages with a synergistic effect. Moreover, chemo-photothermal therapy with CuCo₂S₄ NCs/CL nanocomposites showed an effective therapeutic effect for arterial inflammation, in vivo. Our work demonstrated that chemo-photothermal therapy could be a promising strategy for the treatment of arterial inflammation against atherosclerosis.     

A Supramolecular Approach to Antimicrobial Surfaces

In this paper, we report on the preparation of Imidazole-functionalized glass surfaces, demonstrating the ability of a dinuclear Cu(II) complex of a macrocyclic ligand to give a “cascade” interaction with the deprotonated forms of grafted imidazole moieties. In this way, we realized a prototypal example of an antimicrobial surface based on a supramolecular approach, obtaining a neat microbicidal effect using low amounts of the described copper complex.     

Growth and characterization of two-dimensional crystals for communication and energy applications

This review article covers the growth and characterization of two-dimensional (2D) crystals of transition metal chalcogenides, h-BN, graphene, etc. The chemical vapor transport method for bulk single crystal growth is discussed in detail. Top-down methods like mechanical and liquid exfoliation and bottom-up methods like chemical vapor deposition and molecular beam epitaxy for mono/few-layer growth are described. The optimal characterization techniques such as optical, atomic force, scanning electron, and Raman spectroscopy for identification of mono/few-layer(s) of the 2D crystals are discussed. In addition, a survey was done for the application of 2D crystals for both creation and deterministic transfer of single-photon sources and photovoltaic systems. Finally, the application of plasmonic nanoantenna was proposed for enhanced solar-to-electrical energy conversion and faster/brighter quantum communication devices.