Nickel‐Catalyzed Cross‐Electrophile Coupling of Aryl Bromides with Pyrimidin‐2‐yl Tosylates

A new protocol for the NiCl₂ ‐catalyzed cross‐electrophile coupling of aryl bromides with pyrimidin‐2‐yl tosylates to give the corresponding C2 ‐arylation pyrimidine derivatives has been developed. This study provides an improvement over previous methods by using pyrimidin‐2‐yl tosylates instead of halides as coupling partners that are stable and easily available.     

基于时变SJC-Copula对商品期货市场间风险传染的探究

分别选取WIND商品指数和CRB指数作为衡量我国商品期货市场及国际商品期货市场综合价格的指标,利用时变SJC-Copula模型构建两者之间的动态相依结构,通过动态的尾部相关系数来探究我国商品期货市场与国际市场间的尾部相关性.实证结果表明,我国商品期货市场与国际市场间的上尾相关性要强于下尾相关性,即当商品期货价格上涨时,两个市场间更易发生风险传染.     

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.     

Quantum reaction dynamics of C(1D) + HD → CH(CD) + D(H) on the ground state potential energy surface

We present accurate quantum dynamic calculations of the reaction C(¹D) + HD on the latest version of the potential energy surface [Zhang et al., J. Chem. Phys. 140, 234301 (2014)]. Using a Chebyshev real wave packet method with full Coriolis coupling, we obtain the initial state‐specified ( ) reaction probabilities, integral cross sections, and rate constants. The resulting probabilities display oscillatory structures due to numerous long‐lived resonances supported by the deep potential well. The calculated rate constants and CD/CH product branching ratio at room temperature are in reasonably good agreement with the experimental measurements.     

Global X2A′ potential energy surface of Li2H and quantum dynamics of H + Li2 (X1Σg+) → Li + LiH (X1Σ+) reaction

A global potential energy surface (PES) for the electronic ground state of Li₂H system is constructed over a large configuration space. About 30 000 ab initio energy points have been calculated by MRCI‐F12 method with aug‐cc‐pVTZ basis set. The neural network method is applied to fit the PES and the root mean square error of the current PES is only 1.296 meV. The reaction dynamics of the title reaction has been carried out by employing time‐dependent wave packet approach with second order split operator on the new PES. The reaction probability, integral cross section and thermal rate constant are obtained from the dynamics calculation. In most of the collision energy regions, the integral cross sections are in well agreement with the results reported by Gao et al. The rate constant calculated from the new PES increases in the temperature range of present investigation.     

High‐Mass MALDI‐MS Analysis for the Investigation of Protein Encapsulation within an Engineered Capsid Forming Protein

Chemical cross‐linking combined with MALDI ‐MS was applied to structural analysis of a protein nanocontainer. Specifically, an engineered variant of lumazine synthase from Aquifex aeolicus (AaLS ‐13) was investigated that self‐assembles into a capsid‐like structure and is known to encapsulate other proteins by Coulombic attraction. Two complementary soft ionization techniques, MALDI ‐MS and native ESI ‐MS , were utilized to map the subunit stoichiometry of the high molecular weight capsid. In accordance with the previously reported cryo‐electron microscopy structure of this protein container, only pentameric subunits were detected. This study highlights the possibility to map subunit stoichiometry via chemical cross‐linking with glutaraldehyde followed by MALDI ‐MS . The same approach was used to study protein‐protein interactions during encapsulation of GFP (+36) by the AaLS ‐13 capsid. Heterocomplexes between GFP (+36) and AaLS ‐13 multimers were not observed when mixed at maximal loading capacity (AalS‐13 monomer:GFP (+36) 4:1). This is in agreement with the known fast encapsulation of GFP (+36) by the protein capsid, which essentially removes any free GFP (+36) from the solution. Exceeding the maximal loading capacity by addition of excess GFP (+36) results in aggregation.     

Unambiguous Determination of Protein Arginine Ionization States in Solution by NMR Spectroscopy

Because arginine residues in proteins are expected to be in their protonated form almost without exception, reports demonstrating that a protein arginine residue is charge‐neutral are rare and potentially controversial. Herein, we present a ¹³C‐detected NMR experiment for probing individual arginine residues in proteins notwithstanding the presence of chemical and conformational exchange effects. In the experiment, the ¹⁵N^η and ¹⁵N^ϵ chemical shifts of an arginine head group are correlated with that of the directly attached ¹³C^ζ. In the resulting spectrum, the number of protons in the arginine head group can be obtained directly from the ¹⁵N–¹H scalar coupling splitting pattern. We applied this method to unambiguously determine the ionization state of the R52 side chain in the photoactive yellow protein from Halorhodospira halophila . Although only three H^η atoms were previously identified by neutron crystallography, we show that R52 is predominantly protonated in solution.     

Matrix valued adaptive cross approximation

A new variant of the Adaptive Cross Approximation (ACA) for approximation of dense block matrices is presented. This algorithm can be applied to matrices arising from the Boundary Element Methods (BEM) for elliptic or Maxwell systems of partial differential equations. The usual interpolation property of the ACA is generalised for the matrix valued case. Some numerical examples demonstrate the efficiency of the new method. The main example will be the electromagnetic scattering problem, that is, the exterior boundary value problem for the Maxwell system. Here, we will show that the matrix valued ACA method works well for high order BEM, and the corresponding high rate of convergence is preserved. Another example shows the efficiency of the new method in comparison with the standard technique, whilst approximating the smoothed version of the matrix valued fundamental solution of the time harmonic Maxwell system. Copyright © 2016 John Wiley & Sons, Ltd.     

Synthesis and Antiviral Evaluation of (1,4-Disubstituted-1,2,3-Triazol)-(E)-2-Methyl-but-2-Enyl Nucleoside Phosphonate Prodrugs

A series of hitherto unknown (1,4-disubstituted-1,2,3-triazol)-(E)-2-methyl-but-2-enyl nucleosides phosphonate prodrugs bearing 4-substituted-1,2,3-triazoles were prepared in a straight approach through an olefin acyclic cross metathesis as the key synthetic step. All novel compounds were evaluated for their antiviral activities against HBV, HIV and SARS-CoV-2. Among these molecules, only compound 15j, a hexadecyloxypropyl (HDP)/(isopropyloxycarbonyl-oxymethyl)-ester (POC) prodrug, showed activity against HBV in Huh7 cell cultures with 62% inhibition at 10 μM, without significant cytotoxicity (IC₅₀ = 66.4 μM in HepG2 cells, IC₅₀ = 43.1 μM in HepG2 cells) at 10 μM.     

光纤水听器相位生成载波解调非线性因素的抑制方法

为了消除非线性因素对相位生成载波解调结果的干扰,降低相位生成载波解调过程中低通滤波器的频响特性对相位生成载波解调结果的影响,该文提出了一种基于扩展卡尔曼滤波椭圆参数估计的相位生成载波微分交叉相乘解调方法。该方法在综合考虑各种非线性因素对相位生成载波微分交叉相乘解调结果的影响的基础上,对传统的相位生成载波微分交叉相乘解调过程进行了改进。经过计算机仿真和实验验证,该文所提出的扩展卡尔曼滤波微分交叉相乘方法能够有效地抑制非线性因素对相位生成载波解调结果的干扰,相比传统的相位生成载波微分交叉相乘方法,其信噪比提高了35.0 d B,总谐波失真降低了30.7 dB,信噪谐波比提高了31.0 dB,且扩展卡尔曼滤波微分交叉相乘方法受解调过程中低通滤波器频响特性的影响较小。