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。     

The Role of Radical Bridges in Polynuclear Single-Molecule Magnets

Employing radical bridges between anisotropic metal ions has been a viable route to achieve high-performance single-molecule magnets (SMMs). While the bridges have been mainly considered for their ability to promote exchange interactions, the crystal-field effect arising from them has not been taken into account explicitly. This lack of consideration may distort the understanding and limit the development of the entire family. To shed light on this aspect, herein we report a theoretical investigation of a series of N -radical-bridged diterbium complexes. It is found that while promoting strong exchange coupling between the terbium ions, the N -radical induces a crystal field that interferes destructively with that of the outer ligands, and thus reduces the overall SMM behavior. Based on the theoretical results, we conclude that the SMM behavior in this series could be further maximized if the crystal field of the outer ligands is designed to be collinear with that of the radical bridge. This conclusion can be generalized to all exchange-coupled SMMs.     

Ultrahigh Loading Copper Single Atom Catalyst for Palladium-free Wacker Oxidation

Wacker oxidation is an industry-adopted process to transform olefins into value-added epoxides and carbonyls. However, traditional Wacker oxidation involves the use of homogeneous palladium and copper catalysts for the olefin addition and reductive elimination. Here, we demonstrated an ultrahigh loading Cu single atom catalyst(14% Cu, mass fraction) for the palladium-free Wacker oxidation of 4-vinylanisole into the corresponding ketone with N-methylhydroxylamine hydrochloride as an additive under mild conditions. Mechanistic studies by ¹⁸O and deuterium isotope labelling revealed a hydrogen shift mechanism in this palladium-free process using N-methylhydroxylamine hydrochloride as the oxygen source. The reaction scope can be further extended to Kucherov oxidation. Our study paves the way to replace noble metal catalysts in the traditional homogeneous processes with single atom catalysts.     

Shedding vortex simulation method based on viscous compensation technology research

Owing to the influence of the viscosity of the flow field, the strength of the shedding vortex decreases gradually in the process of backward propagation. Large-scale vortexes constantly break up, forming smaller vortexes. In engineering, when numerical simulation of vortex evolution process is carried out, a large grid is needed to be arranged in the area of outflow field far from the boundary layer in order to ensure the calculation efficiency. As a result, small scale vortexes at the far end of the flow field cannot be captured by the sparse grid in this region, resulting in the dissipation or even disappearance of vortexes. In this paper, the effect of grid scale is quantified and compared with the viscous effect through theoretical derivation. The theoretical relationship between the mesh viscosity and the original viscosity of the flow field is established, and the viscosity term in the turbulence model is modified. This method proves to be able to effectively improve the intensity of small-scale shedding vortexes at the far end of the flow field under the condition of sparse grid. The error between the simulation results and the results obtained by using fine mesh is greatly reduced, the calculation time is shortened, and the high-precision and efficient simulation of the flow field is realized.     

Design,synthesis and evaluation of novel dehydroabietic acid-dithiocarbamate hybrids as potential multi-targeted compounds for tumor cytotoxicity

In the present study, novel representatives of the important group of biologically-active, dehydroabietic acid-bearing dithiocarbamate moiety, were synthesized and characterized by ¹H NMR, ¹³C NMR, HR-MS. The in vitro antiproliferative activity evaluation (MTT) indicated that these compounds exhibited potent inhibitory activities in various cancer cell lines (HepG-2, MCF-7, HeLa, T-24, MGC-803). Particularly, compound III-b possessed extraordinary cytotoxicity with low micromolar IC₅₀ values ranging from 4.07 to 38.84 µM against tested cancer cell lines, while displayed weak cytotoxicity on two normal cell lines (LO-2 and HEK 293 T). Subsequently, the potential mechanisms of representative compound III-b were elementarily investigated by Transwell experiment, which showed III-b can inhibit cancer cells migration. Annexin-V/PI dual staining showed that the compound can induce HepG-2 cells apoptosis in a dose-dependent manner. Meanwhile this apoptosis may be related to the upregulated protein expression of cleaved-caspase 3, cleaved-caspase 9, Bax and downregulated of Bcl-2 indicated by Western Blot. Later study further confirmed that ROS levels in HepG-2 cells increased significantly with the rise of concentrations. In addition, through the network pharmacology data analyzing, the core targets and signaling pathways of compound III-b for treatment of liver neoplasms were forecasted. Molecular docking model showed that compound III-b had high affinity with hub targets (CASP3, EGFR, HSP90AA1, MAPK1, ERBB2, MDM2), suggesting that compound III-b might target the hub protein to modulate signaling activity. Taken together, these data indicated that dehydroabietic acid structural modification following the “Molecular hybridization” principle is a feasible way to discover the potential multi-targeted antitumor compounds.     

Molecular and colloidal self-assembly at the oil–water interface

Self-assembly is a versatile bottom-up approach for fabricating novel supramolecular materials with well-defined nano- or micro-structures associated with functionalities. The oil-water interface provides an ideal venue for molecular and colloidal self-assembly. This paper gives an overview of various self-assembled materials, including nanoparticles, polymers, proteins, and lipids, at the oil-water interface. Focus has been given to fundamental principles and strategies for engineering the self-assembly process, such as control of pH, ionic strength and use of external fields, to achieve complex soft materials with desired functionalities, such as nanoparticle surfactants, structured liquids, and proteinosomes. It has been shown that self-assembly at the oil-water interface holds great promise for developing well-structured complex materials useful for many research and industrial applications.     

Metamorphic InAs(Sb)/InGaAs/InAlAs nanoheterostructures grown on GaAs for efficient mid-IR emitters

High-efficiency semiconductor lasers and light-emitting diodes operating in the 3–5?μm mid-infrared (mid-IR) spectral range are currently of great demand for a wide variety of applications, in particular, gas sensing, noninvasive medical tests, IR spectroscopy etc. III-V compounds with a lattice constant of about 6.1?Å are traditionally used for this spectral range. The attractive idea to fabricate such emitters on GaAs substrates by using In(Ga,Al)As compounds is restricted by either the minimum operating wavelength of ～8?μm in case of pseudomorphic AlGaAs-based quantum cascade lasers or requires utilization of thick metamorphic In_xAl_1-xAs buffer layers (MBLs) playing a key role in reducing the density of threading dislocations (TDs) in an active region, which otherwise result in a strong decay of the quantum efficiency of such mid-IR emitters. In this review we present the results of careful investigations of employing the convex-graded In_xAl_1-xAs MBLs for fabrication by molecular beam epitaxy on GaAs (001) substrates of In(Ga,Al)As heterostructures with a combined type-II/type-I InSb/InAs/InGaAs quantum well (QW) for efficient mid-IR emitters (3–3.6?μm). The issues of strain relaxation, elastic stress balance, efficiency of radiative and non-radiative recombination at T?=?10–300?K are discussed in relation to molecular beam epitaxy (MBE) growth conditions and designs of the structures. A wide complex of techniques including in-situ reflection high-energy electron diffraction, atomic force microscopy (AFM), scanning and transmission electron microscopies, X-ray diffractometry, reciprocal space mapping, selective area electron diffraction, as well as photoluminescence (PL) and Fourier-transformed infrared spectroscopy was used to study in detail structural and optical properties of the metamorphic QW structures. Optimization of the growth conditions (the substrate temperature, the As₄/III ratio) and elastic strain profiles governed by variation of an inverse step in the In content profile between the MBL and the InAlAs virtual substrate results in decrease in the TD density (down to 3?×?10⁷ cm^?2), increase of the thickness of the low-TD-density near-surface MBL region to 250–300?nm, the extremely low surface roughness with the RMS value of 1.6–2.4?nm, measured by AFM, as well as rather high 3.5?μm-PL intensity at temperatures up to 300?K in such structures. The obtained results indicate that the metamorphic InSb/In(Ga,Al)As QW heterostructures of proper design, grown under the optimum MBE conditions, are very promising for fabricating the efficient mid-IR emitters on a GaAs platform.     

A review of recent advances in catalytic combustion of VOCs on perovskite-type catalysts

Along with the rapid development of industry, VOCs gradually move into the spotlight, and now become a kind of harmful environmental pollutants that cannot be overlooked. This paper introduces the hazards of VOCs and the common catalytic combustion catalysts, noble metal catalysts and non-noble metal catalysts, for the elimination of VOCs. Perovskite catalysts, as one of the non-noble catalysts, play an important role in the field of catalytic combustion in recent years. According to the classification of elements doping in perovskites, the research achievements in the past five years were analyzed and reviewed. In addition, this paper also analyzes and elaborates the reaction kinetics and QSAR/QSPR models for the introduction of structural properties and reaction mechanisms.     

Comparative Study of Alkali-Cation-Based (Li+, Na+, K+) Electrolytes in Acetonitrile and Alkylcarbonates

The development of a suitable functional electrolyte is urgently required for fast-charging and high-voltage alkali-ion (Li, Na, K) batteries as well as next-generation hybrids supercapacitors. Many recent works focused on an optimal selection of electrolytes for alkali-ion based systems and their electrochemical performance but the understanding of the fundamental aspect that explains their different behaviour is rare. Herein, we report a comparative study of transport properties for LiPF₆, NaPF₆, KPF₆ in acetonitrile (AN) and a binary mixture of ethylene carbonate (EC), dimethyl carbonate (DMC): (EC/DMC : 1/1, weigh) through conductivities, densities and viscosities measurements in wide temperature domain. By application of the Stokes-Einstein, Nernst-Einstein, and Jones Dole equations, the effective ionic solvated radius of cation (r_eff), the ionic dissociation coefficient (α_D) and structuring Jones Dole's parameters (A, B) for salt are calculated and discussed according to solvent or cation nature as a function of temperature. From the results, we demonstrate that better mobility of potassium can be explained by the nature of the ion-ion and ion-solvent interactions due to its polarizability. In the same time, the predominance of triple ions in the case of K⁺, is a disadvantage at high concentration.     

Prediction of drug-target interaction by integrating diverse heterogeneous information source with multiple kernel learning and clustering methods

BackgroundIdentification of potential drug-target interaction pairs is very important for pharmaceutical innovation and drug discovery. Numerous machine learning-based and network-based algorithms have been developed for predicting drug-target interactions. However, large-scale pharmacological, genomic and chemical datum emerged recently provide new opportunity for further heightening the accuracy of drug-target interactions prediction.ResultsIn this work, based on the assumption that similar drugs tend to interact with similar proteins and vice versa, we developed a novel computational method (namely MKLC-BiRW) to predict new drug-target interactions. MKLC-BiRW integrates diverse drug-related and target-related heterogeneous information source by using the multiple kernel learning and clustering methods to generate the drug and target similarity matrices, in which the low similarity elements are set to zero to build the drug and target similarity correction networks. By incorporating these drug and target similarity correction networks with known drug-target interaction bipartite graph, MKLC-BiRW constructs the heterogeneous network on which Bi-random walk algorithm is adopted to infer the potential drug-target interactions.ConclusionsCompared with other existing state-of-the-art methods, MKLC-BiRW achieves the best performance in terms of AUC and AUPR. MKLC-BiRW can effectively predict the potential drug-target interactions.