Lysosome‐targeted potent half‐sandwich iridium(III) α‐diimine antitumor complexes

Fifteen organometallic Ir(III) half‐sandwich complexes ( 1A – 5C ) having the general formula [(η⁵‐Cp^x)Ir(N^N)Cl]PF₆ (Cp^x = Cp*, tetramethyl(phenyl)cyclopentadienyl (Cp^xph) or tetramethyl(biphenyl)cyclopentadienyl (Cp^xbiph); N^N = diamine) have been synthesized and characterized. The molecular structure of 1A was determined using single‐crystal X‐ray diffraction analysis. The hydrolysis of 1A – 5C was monitored using UV–visible spectra. Complexes 3A – 3C showed catalytic activity for the oxidation of NADH to NAD⁺, where 3C showed the highest turnover number of 29.9 within 450 min. Cytotoxicity examination by MTT assay was carried out against two human cancer cell lines (HeLa and A549) after 24 or 48 h drug treatment. The complexes showed high potency, where the most potent complex ( 3C ; IC₅₀ = 3.4 μM) was six times more active than cisplatin against A549 cells after 24 h drug exposure. Cytotoxic potency towards A549 cells increased with phenyl substitution on Cp ring: Cp^xbiph > Cp^xph > Cp*. In addition, the biological studies showed that 3C caused cell apoptosis and cell cycle arrest at G₁ phase in A549 cancer cells. Moreover, 3C increased the level of reactive oxygen species markedly after 24 h, which may provide an important basis for killing cancer cells. Confocal laser scanning microscopy was used to track 3C in A549 cells. The cellular localization experiment showed that 3C targeted lysosomes and caused lysosomal damage.     

Estimation of partially specified spatial panel data models with random-effects

In this article, we study estimation of a partially specified spatial panel data linear regression with random-effects. Under the conditions of exogenous spatial weighting matrix and exogenous regressors, we give an instrumental variable estimation. Under certain sufficient assumptions, we show that the proposed estimator for the finite dimensional parameter is root-N consistent and asymptotically normally distributed and the proposed estimator for the unknown function is consistent and asymptotically distributed. Consistent estimators for the asymptotic variance-covariance matrices of both the parametric and unknown components are provided. The Monte Carlo simulation results verify our theory and suggest that the approach has some practical value.     

爆炸荷载作用下方形夹芯板动力学响应与优化设计数值分析

为研究方形蜂窝铝板在爆炸荷载作用下的动力学响应,基于LS-DYNA非线性有限元软件,建立了TNT炸药-前后面板-蜂窝夹芯-空气的三维有限元模型。采用ALE(任意的拉格朗日欧拉)多物质流固耦合算法分析了蜂窝铝板在冲击荷载作用下的变形机理、塑性变形、能量吸收以及结构的优化。数值模拟结果表明:随着面板厚度、核心高度的增加,蜂窝铝板在冲击荷载作用下的塑性变形明显减小,抵抗变形的能力增强;随着爆轰入射角度的增加,结构的破坏程度有所减小,入射角越大这种效果越发明显。对结构给定边长和受冲击面积以及面板厚度配合比、夹芯量纲为一的高度进行了局部的优化分析,为设计优质铝蜂窝板提供参考。     

Sandwich-like Catalyst–Carbon–Catalyst Trilayer Structure as a Compact 2D Host for Highly Stable Lithium–Sulfur Batteries

Herein, we propose the construction of a sandwich-structured host filled with continuous 2D catalysis–conduction interfaces. This MoN-C-MoN trilayer architecture causes the strong conformal adsorption of S/Li₂S_x and its high-efficiency conversion on the two-sided nitride polar surfaces, which are supplied with high-flux electron transfer from the buried carbon interlayer. The 3D self-assembly of these 2D sandwich structures further reinforces the interconnection of conductive and catalytic networks. The maximized exposure of adsorptive/catalytic planes endows the MoN-C@S electrode with excellent cycling stability and high rate performance even under high S loading and low host surface area. The high conductivity of this trilayer texture does not compromise the capacity retention after the S content is increased. Such a job-synergistic mode between catalytic and conductive functions guarantees the homogeneous deposition of S/Li₂S_x, and avoids thick and devitalized accumulation (electrode passivation) even after high-rate and long-term cycling.     

Fatigue Behavior of Composite Sandwich Panels Under Three Point Bending Load

In this paper, the bending fatigue tests of honeycomb sandwich panels are carried out by using an improved three-point bending test fixture, and the S-N curves at different stress ratios are obtained. Through the records of fatigue damage in the experiment, the failure mode of the honeycomb sandwich panels and the source of fatigue damage are determined. At the same time, through the calculation of the shear stress distribution on the honeycomb wall, the reasons for the difference in the failure morphology of the L-direction and W-direction sandwich panels are clarified. Besides, a life prediction method is proposed and its effectiveness in predicting the fatigue life of sandwich panels has been verified.     

Ansa‐Bridged Bis(benzene) Titanium Complexes

Taking advantage of an improved synthesis of [Ti(η⁶‐C₆H₆)₂], we report here the first examples of ansa‐bridged bis(benzene) titanium complexes. Deprotonation of [Ti(η⁶‐C₆H₆)₂] with nBuLi in the presence of N,N,N′,N′′,N′′‐pentamethyldiethylenetriamine (pmdta) leads to the corresponding 1,1′‐dilithio salt [Ti(η⁶‐C₆H₅Li)₂] ? pmdta that enables the preparation of the first one‐ and two‐atom‐bridged complexes by simple salt metathesis. The ansa complexes were fully characterized (NMR spectroscopy, UV/Vis spectroscopy, elemental analysis, and X‐ray crystallography) and further studied electrochemically and computationally. Moreover, [Ti(η⁶‐C₆H₆)₂] is found to react with the Lewis base 1,3‐dimethylimidazole‐2‐ylidene (IMe) to give the bent sandwich complex [Ti(η⁶‐C₆H₆)₂(IMe)].     

Ansa‐Complexes of [Mn(η5‐C5H5)(η6‐C6H6)]: Preparation,Characterization, and Reactivity of [n]Manganoarenophanes (n=1, 2, 3)

We report the synthesis of [n]manganoarenophanes (n=1, 2) featuring boron, silicon, germanium, and tin as ansa‐bridging elements. Their preparation was achieved by salt‐elimination reactions of the dilithiated precursor [Mn(η⁵‐C₅H₄Li)(η⁶‐C₆H₅Li)]?pmdta (pmdta=N,N,N′,N′,N′′‐pentamethyldiethylenetriamine) with corresponding element dichlorides. Besides characterization by multinuclear NMR spectroscopy and elemental analysis, the identity of two single‐atom‐bridged derivatives, [Mn(η⁵‐C₅H₄)(η⁶‐C₆H₅)SntBu₂] and [Mn(η⁵‐C₅H₄)(η⁶‐C₆H₅)SiPh₂], could also be determined by X‐ray structural analysis. We investigated for the first time the reactivity of these ansa‐cyclopentadienyl–benzene manganese compounds. The reaction of the distannyl‐bridged complex [Mn(η⁵‐C₅H₄)(η⁶‐C₆H₅)Sn₂tBu₄] with elemental sulfur was shown to proceed through the expected oxidative addition of the Sn?Sn bond to give a triatomic ansa‐bridge. The investigation of the ring‐opening polymerization (ROP) capability of [Mn(η⁵‐C₅H₄)(η⁶‐C₆H₅)SntBu₂] with [Pt(PEt₃)₃] showed that an unexpected, unselective insertion into the C_ipso?Sn bonds of [Mn(η⁵‐C₅H₄)(η⁶‐C₆H₅)SntBu₂] had occurred.     

一种面板数据分位数回归模型的工具变量方法

本文将工具变量分位数回归模型(IVQR)应用到面板数据中,结合Canay对面板分位数回归的两步估计法以及Chernozhukov对IVQR模型的估计方法,提出了两步面板分位数工具变量估计法(2S-IVFEQR),并给出相应的参数估计。本文提出的方法较已有的方法计算复杂度低,蒙特卡洛模拟结果显示在数据量不大或者处理长面板数据时,2S-IVFEQR方法要优于传统的IVFEQR方法,且运算时间短。     

基于面板模型的商品房价格影响因素的实证研究

选取了我国30个省市2006~2015年的面板数据,应用面板数据计量模型回归的方法,基于R语言对影响商品房价格的因素进行实证研究.首先,经过Hausman检验与F检验确定面板数据的模型为混合估计模型;模型可以通过十折交叉验证法、残差正太性的检验、Q-Q图检验、变量间共线性的检验;最后经过逐步回归分析,结果表明土地价格、商品房销售面积、居民可支配收入、人均国内总产值财政收入占地区生产总值比重、汇率这6个指标对商品房价格都有显著性的影响.其中,土地价格和居民可支配收入对商品房价格的影响最为突出.     

Panel‐based stratified cluster sampling and analysis for photovoltaic outdoor measurements

We study a stratified multisite cluster‐sampling panel time series approach in order to analyse and evaluate the quality and reliability of produced items, motivated by the problem to sample and analyse multisite outdoor measurements from photovoltaic systems. The specific stratified sampling in spatial clusters reduces sampling costs and allows for heterogeneity as well as for the analysis of spatial correlations due to defects and damages that tend to occur in clusters. The analysis is based on weighted least squares using data‐dependent weights. We show that this does not affect consistency and asymptotic normality of the least squares estimator under the proposed sampling design under general conditions. The estimation of the relevant variance–covariance matrices is discussed in detail for various models including nested designs and random effects. The strata corresponding to damages or manufacturers are modelled via a quality feature by means of a threshold approach. The analysis of outdoor electroluminescence images shows that spatial correlations and local clusters may arise in such photovoltaic data. Further, relevant statistics such as the mean pixel intensity cannot be assumed to follow a Gaussian law. We investigate the proposed inferential tools in detail by simulations in order to assess the influence of spatial cluster correlations and serial correlations on the test's size and power. ©2016 The Authors. Applied Stochastic Models in Business and Industry published by John Wiley & Sons, Ltd.