Regiocontrol in the oxidative Heck reaction of indole by ligand-enabled switch of the regioselectivity-determining step

Efficient control of regioselectivity is a key concern in transition-metal-catalyzed direct C–H functionalization reactions. Various strategies for regiocontrol have been established by tuning the selectivity of the C–H activation step as a common mode. Herein, we present our study on an alternative mode of regiocontrol, in which the selectivity of the C–H activation step is no longer a key concern. We found that, in a reaction where the C–H activation step exhibits a different regio-preference from the subsequent functionalization step, a ligand-enabled switch of the regioselectivity-determining step could provide efficient regiocontrol. This mode has been exemplified by the Pd(ii)-catalyzed aerobic oxidative Heck reaction of indoles, in which a ligand-controlled C3-/C2-selectivity was achieved for the first time by the development of sulfoxide-2-hydroxypyridine (SOHP) ligands.

Ligand-enabled switch of the regioselectivity-determining step allowed for efficient regiocontrol in the aerobic oxidative Heck reaction of indole.     

运用Actigraph GT3X三轴加速度传感器测量成年及老年男性人群步行的信效度研究

评价Actigraph GT3X三轴加速度传感器测量中国男性人群典型体力互动信效度,开发基于中国人群步行活动模式的GT3X三轴加速度传感器能耗推算方程。方法受试对象包括青年组(21.92±1.14岁),老年组(55.5±4.52岁)。受试者佩戴GT3X三轴加速度传感器,在跑台上分别完成3km/h(慢走)、4.5km/h(正常步行)、4.5km/h10%(上坡步行)、6km/h(快走)以及7.5km/h(慢跑)速度的走跑运动各5min。受试者佩戴COSMED K4b2便携式代谢测试仪,并将GT3X三轴加速度传感器佩戴于髋部,同步采集心肺功能仪及加速度传感器数据。结果根据受试对象4种无坡度走跑运动推导出线性方程MET=0.000653*counts(Axis1)+2.345521以及线性方程MET=0.000689*counts(VM)+1.640721,但其相关系数不高;GT3X+三轴加速度传感器记录上坡步行(4.5km/h10%)运动与无坡度运动(4.5km/h)相比,三轴counts及VM均显示有差异性(P<0.05),但counts增加率远低于MET增加率;GT3X+三轴加速度传感器两次重复测试,pearson值高,即离散程度低。结论本研究推导垂直轴(Axis1)、三轴矢量和(VM)的线性方程,为中度相关,误差值较大,且上坡运动时的GT3X+三轴加速度传感器记录counts值与MET值呈非线性相关,提示Actigraph GT3X三轴加速度传感器能耗推算方程可根据不同运动方式、运动强度推算相对应方程;Actigraph GT3X三轴加速度传感器测量我国成年及老年男性人群步行活动其信度较高。     

A multiaxial elastic potential with error-minimizing approximation to rubberlike elasticity

This study is concerned with a new,explicit approach by means of which forms of the large strain elastic potential for multiaxial rubberlike elasticity may be obtained based on data for a single deformation mode.As a departure from usual studies,here for the first time errors may be estimated and rendered minimal for all possible deformation modes and,furthermore,failure behavior may be incorporated.Numerical examples presented are in accurate agreement with Treloar's well-known data.     

12β-Acetyloxyperforatin,a New Limonoid from Harrisonia Perforata

A new A, D-seco limonoid, named 12-acetyloxyperforatin (1), along with three known ones, were isolated from the leaves of Harrisonia perforata. Their structures were elucidated on the basis of spectroscopic analysis, including extensive NMR techniques and computational modelling. These compounds showed no inhibitory activity against the 11β-HSD1 enzyme.     

基于修正斜压场的RC框架边节点剪切性能分析

为研究钢筋屈服强度和混凝土抗压强度对钢筋混凝土(RC)框架边节点剪切性能的影响规律,基于修正斜压场理论(MCFT),对某框架边节点的剪切应力-应变骨架曲线进行数值模拟,并与试验结果进行对比.在验证MCFT算法的精度后,研究钢筋屈服强度和混凝土抗压强度两个参数变化对RC框架边节点剪切应力-应变骨架曲线和峰值剪切应力的影响规律.结果表明:基于MCFT可以较好地模拟RC框架边节点的剪切应力-应变关系曲线; RC框架边节点的峰值剪切应力对混凝土抗压强度的变化更为敏感,但当试件的钢筋(HRB400)屈服应力下降幅度超过16.45%时,对钢筋屈服应力的变化更为敏感;当试件的钢筋(HRB400)屈服应力下降幅度超过10%时,节点发生钢筋滑移破坏,此时峰值剪切应力会大幅下降.     

紫色球杆菌视紫红质光谱特性的机器学习研究

近年来，机器学习等人工智能技术被应用于蛋白质工程，其在蛋白质结构、功能预测、催化活性等研究中具有独特优势。在未知蛋白质结构的情况下，将蛋白质序列和功能特性与机器学习相结合，基于序列-活性关系（innovative sequence-activity relationship，ISAR）算法，将蛋白质氨基酸序列数字化，用快速傅里叶变换（fast four transform，FFT）进行预处理，再进行偏最小二乘回归建模，可在数据集较少情况下拟合得到最佳模型。通过机器学习对紫色球杆菌视紫红质（gloeobacter violaceus rhodopsin，GR）的突变体蛋白质氨基酸序列与光谱最大吸收波长进行建模，获得了最佳模型。用最佳索引LEVM760106建模得到的确定系数R² 为0.944，均方误差E为11.64。用小波变换进行的预处理，其R² 虽也约为0.944，但E大于11.64，不及FFT进行的预处理。方法较好地解决了蛋白质序列与功能特性之间的数学建模问题，在蛋白质工程中可为预测更优的突变体提供支持。     

凋亡抑制蛋白与肿瘤关系的研究

凋亡抑制蛋白(inhibitor of apoptosis proteins,IAPs)可以作为癌症诊断和治疗的靶点,在肿瘤研究方面备受关注,就凋亡抑制蛋白的结构、功能、在肿瘤中的表达与肿瘤的关系等研究进展作一综述,为凋亡抑制蛋白的研究提供信息和思路.