XANES/EPR Evidence of the Oxidation of Nickel(II) Quinolinylpropioamide and Its Application in Csp3−H Functionalization

An in situ generated oxidation species of nickel quinolinylpropioamide intermediate was produced. Characterization by X-ray absorption near edge structure (XANES) and EPR provides complementary insights into this oxidized nickel species. With aliphatic amides and isocyanides as substrates, a nickel-catalyzed facile synthesis of structurally diverse five-membered lactams could be achieved.     

QEPAS系统中石英音叉模态仿真计算与研究

对石英音叉增强型光声光谱(QEPAS)系统中常用的石英音叉进行了有限元模态计算，获得石英音叉前6阶振型与模态频率，认知了第4阶对称摆动振型为有效振动，利用单因素法分析了石英音叉的音臂长度l₁、音臂宽度w₁、音臂厚度t、音臂切角θ、音臂圆孔直径d及音臂圆孔高度h对低阶有效共振频率(Fre)的影响，敏感度依次为： l₁> w₁>d>θ>t>h，考虑实际设计情形，筛选出了l₁，w₁，d与h四个石英音叉设计变量，采用Box-Behnken实验设计方案与RSM(response surface methodology)方法，以Fre为函数目标，建立l₁，w₁，d与h的二次回归响应面模型，得到了参数之间的交互作用，利用Design-Expert软件对响应面模型进行设计参数反求，结果表明，在15 000 Hz≤Fre≤25 000 Hz计算区域内误差较小，基本满足QEPAS系统的计算需求，所提出的研究与设计方法具有一定通用性，可为QEPAS系统中石英音叉结构参数设计提供参考。     

Two new aromadendrane sesquiterpenes from Verticillium psalliotae

The chemical constituents of the fungus Verticillium psalliotae were studied. Two new aromadendrane sesquiterpenes inonotin M (1) and inonotin N (2) were isolated from the EtOAc extract of the fungal culture broth. The structures of compounds were elucidated mainly by HRESIMS experiments, and 1D, 2D-NMR spectroscopy analysis.     

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.     

Improving the gas barrier,mechanical and thermal properties of poly(vinyl alcohol) with molybdenum disulfide nanosheets

New multifunctional materials with both high structural and gas barrier performances are important for a range of applications. Herein we present a one‐step mechanochemical process to prepare molybdenum disulfide (MoS₂) nanosheets with hydroxy functional groups that can simultaneously improve mechanical strength, thermal conductivity, and gas permittivity of a polymer composite. By homogeneously incorporating these functionalized MoS₂ nanosheets at low loading of less than 1 vol %, a poly(vinyl alcohol) (PVA) polymer exhibits elongation at break of 154%, toughness of 82 MJ/m³, and in‐plane thermal conductivity of 2.31 W/m K. Furthermore, this composite exhibits significant gas barrier performance, reducing the permeability of helium by 95%. Under fire condition, the MoS₂ nanosheets form thermally stable char, thus enhancing the material's resistance to fire. Hydrogen bonding has been identified as the main interaction mechanism between the nanofillers and the polymer matrix. The present results suggest that the PVA composite reinforced with 2D layered nanomaterial offers great potentials in packaging and fire retardant applications. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 406–414     

Synthesis of μ2-Oxo-Bridged Iron(III) Tetraphenylporphyrin–Spacer–Nitroxide Dimers and their Structural and Dynamics Characterization by using EPR and MD Simulations

Iron(III) porphyrins have the propensity to form μ₂-oxo-dimers, the structures of which resemble two wheels on an axle. Whereas their crystal structure is known, their solution structure and internal dynamics is not. In the present work, the structure and dynamics of such dimers were studied by means of electron paramagnetic resonance (EPR) spectroscopy and quantum chemistry based molecular dynamics (MD) simulations by using the semiempirical tight-binding method (GFN-xTB). To enable EPR investigation of the dimers, a nitroxide was attached to each of the tetraphenylporphyrin cores through a linear and a bent linker. The inter-nitroxide distance distributions within the dimers were determined by continuous-wave (cw)-EPR and pulsed electron–electron double resonance (PELDOR or DEER) experiments and, with the help of MD, interpreted in terms of the rotation of the porphyrin planes with respect to each other around the Fe–O–Fe axis. It was found that such rotation is restricted to the four registers defined by the phenyl substituents. Within the registers, the rotation angle swings between 30° and 60° in the proximal and between 125° and 145° in the distal register. With EPR, all four angles were found to be equally populated, whereas the 30° and 145° angles are strongly favored to the expense of the 60° and 125° angles in the MD simulation. In either case, the internal dynamics of these dimers thus resemble the motion of a step motor.     

基于电化学发光和阻抗技术研究DNA单碱基错配

单碱基错配的识别和稳定性差异在核酸多态性研究中至关重要。在同一电化学传感器平台上，采用电化学发光（ECL）和电化学阻抗（EIS）2种技术，协同研究DNA链中不同类型和不同位点的单碱基错配识别和稳定性差异。电极表面具有茎环构象的探针DNA与完全互补DNA、不同类型或不同位点单碱基错配DNA杂交前后的ECL和EIS信号强度变化有显著差异。信号强度变化可揭示单碱基错配识别的稳定性。结果表明，DNA链中心位点的C-A单碱基错配稳定性低于链两端的，靠近键合电极表面双链链端的C-A单碱基错配稳定性低于非键合电极表面双链链端的，同一中心位点C-X碱基对的稳定性顺序为C-G?C-T>C-A≥C-C。研究结果可为核酸多态性研究提供参考。     

原子系综中光学腔增强的Duan-Lukin-Cirac-Zoller写过程激发实验

原子系综中的Duan-Lukin-Cirac-Zoller(DLCZ)过程是产生光与原子(量子界面)量子关联和纠缠的重要手段.当一束写光与原子发生作用时,将会产生斯托克斯(Stokes)光子的自发拉曼散射,并同时产生一个自旋波(spin-wave)存储在原子系综中,上述过程即为DLCZ量子记忆产生过程.这一过程被广泛地研究.本文将87Rb原子系综放入驻波腔,并使Stokes光子与光学腔共振,我们观察到有腔且锁定的情况下Stokes光子产生概率比无腔时增大了8.7倍.在此条件下研究了Stokes光子产生概率和写光功率的关系,Stokes光子产生概率随写光功率线性增大.     

A Stable Porphyrin Functionalized Graphite Electrode Used at the Oxygen Evolution Reaction Potential

Many researches have been devoted to rechargeable power generators that can store (but also release) energy. This availability is ensured through (e. g.) the oxygen evolution reaction (OER). However, (i) large values of the overpotentials and (ii) a progressive detriment of the anode (graphite) electrode limit the ultimate device. In view of enhancing the electrode performances, graphite was protected by following different strategies, which oblige to follow precise preparation protocols. Here, we prove that a thin layer of free-base porphyrin molecules is able to protect the underneath graphite electrode from detriment even if many (about 100) electrochemical cycles are performed.