Synthesis of 3-substituted 8,9-didehydroazepino[4,5-b]indolines via ring expansion reaction of pyrroloindolines

An unexpected ring expansion reaction was observed to give the 3-substituted 8,9-didehydroazepinoindolines when 3-substituted pyrroloindolines reacted with electron-deficient acetylenes in the presence of catalytic amount of CuI. The ring expansion reaction proceeded via a three-step one-pot cascade pathway of aza-Michael-addition/ring-opening/iminium-cyclization.     

木榄醇手性光谱的密度泛函研究

手性光学理论研究有助于解释手性分子的旋光机理和设计新的手性药物.采用B3LYP方法,计算了木榄醇A—C的旋光度和圆二色谱.从分子结构、正则振动和电子结构方面,探索了分子手性微观起源,分析了旋光度和电子圆二色谱的溶剂效应.表明OH的引入可调节分子的手性,甲基和苯环加强了分子的手性.发生在手性骨架上的振动和电子跃迁,加强了分子的手性.溶剂效应减小旋光度、削弱电子圆二色谱. 关键词： 木榄醇 光学活性 密度泛函理论 圆二色谱     

Brainin A,a novel flavanol from Brainea insignis

A novel flavanol bearing phenylpropionic acid moiety at C-4 through a C-C bonding,named brainin A(1),was isolated from the rhizomes of Brainea insignis.Its structure was elucidated on the basis of spectral data including 2D NMR and HR-ESI-MS.     

极端中和表型HIV包膜蛋白gp120的高温分子动力学模拟研究

作为HIV侵染细胞的蛋白质机器,包膜蛋白gp120利用序列变异和结构柔性等策略逃避宿主免疫识别,是病毒呈现出不同中和表型的主要原因.尽管HIV中和表型的分子机制已被初步探索,但其热力学相关的分子基础仍待进一步阐明.本研究利用同源模建的方法构建了极端中和表型HIV毒株(中和抵抗毒株H061.14与中和敏感毒株R2)的gp120结构模型,在逐渐升高的温度梯度下进行了高温分子动力学模拟,以研究二者在结构稳定性、解折叠和构象柔性上的差异.结果表明,HIV中和表型与gp120的热力学性质呈正相关,与解折叠程度无必然关联.各温度下gp120的结构偏差、天然接触含量、构象群体分布,以及单残基柔性的比较清楚地说明,中和敏感比中和抵抗gp120表现出更大的结构偏差、更多的构象状态和更高的构象柔性,但两者具有相似的解折叠程度.由极端中和表型HIV包膜蛋白gp120显著不同的热力学性质可以推断,HIV很可能利用gp120的热力学性质来调节其构象,进而平衡病毒侵染和免疫逃避之间的矛盾.我们的研究不仅揭示了极端中和表型HIV包膜蛋白gp120的在构象柔性和结构稳定性上的差异,同时还从高温解折叠热力学的角度明确了...     

Electronic circular dichroism of some double-helical alkynyl cyclophanes with 1,1′-binaphthyl auxiliaries investigated using time-dependent density functional calculations

For several double-helical molecules, the dependence of electronic circular dichroism (ECD) spectra on the molecular and electronic structures is investigated on the basis of TDDFT computations with the B3LYP hybrid functional. The calculations of a model molecule reveal that an acute-angled rotational dihedral angle other than an obtuse-angled rotational dihedral angle between two naphthyls implies Davydov splitting of exciton coupling. For the R enantiomers, the acute-angled rotational dihedral angle implies a negative lowest-energy Cotton effect, which is induced by electron density transfer from binaphthyls to phenyethynyls in the S_0?→?S₄ excitations. Due to the large positive rotational strength of the S_0?→?S₁ transition, the lowest-energy Cotton effect of the simplest cyclophane R-1 is positive, where the electron density transfer from phenyethynyls to binaphthyls plays an important role.     

滇中三类典型地表植被的机载高光谱特征分析

高光谱遥感技术因为具有图谱合一的优势,并且相较于传统多光谱遥感技术,可以实现对目标的精确识别,逐渐运用于地表植被的探测。选择以滇中地区的竹林、华山松、杂木林这三类典型地表植被为研究对象,基于机载高光谱影像数据,通过对原始高光谱、一阶微分处理光谱、连续统去除处理光谱进行处理与对比分析,获得滇中三类典型地表植被类型高光谱特征的初步探测认识。主要结果包括：(1）基于对原始光谱特征分析得出,三类典型地表植被的原始高光谱的最佳波段窗口出现在690~946 nm,且在该波段范围内光谱反射率特征为竹林>华山松>杂木林;(2）运用一阶微分处理光谱特征分析得出,利用光谱微分变换处理能够增强植被的光谱差异。经过一阶微分处理后光谱的最佳波段窗口出现在670~774 nm,在该波段范围内的一阶微分系数为竹林>华山松>杂木林。且发现718 nm为三类植被的敏感波段,即可用718 nm敏感特征波段区分开三类植被类型;并且综合运用一阶微分光谱特征参数中的红边位置,蓝边幅值、黄边幅值、红边幅值、蓝边面积、黄边面积和红边面积可以将三类植被类型进行区分;(3）最后基于连续统去除处理光谱特征分析得出,连续统去除方法能够有效地增强植被光谱曲线反射和吸收的特征。经过连续统去除处理后的光谱,三类典型植被的最佳波段窗口在458~554和570~690 nm,这两个波段范围内的连续统去除系数均为竹林>华山松>杂木林,且发现502和674 nm为三类典型植被的敏感波段,即可用此特征综合区分三类植被类型。该研究结果有助于对滇中森林植被精细判别提供技术方法,同时,为今后发展天-地-空的高光谱影像数据一体化遥感植被精细分类提供技术支撑。     

Unexpected synthesis of structure-tunable AIE-active acrylonitriles by simple temperature variation for bioimaging

<正>Small molecule-based fluorescence imaging is an indispensable tool for direct visualization and dynamic tracking of important biological species in live samples,due to its excellent sensitivity,remarkable selectivity,easy and fast acquisition,and non-invasive property [1,2].In comparison with one-photon fluorescence imaging,two-photon fluorescence imaging is highly preferable because of pulsed nearinfrared (NIR) laser irradiation,resulting in minimal back-     

电磁场法向边值关系的严密数学理论

阐述了矢量场穿过2阶无穷小平面的通量虽然也是2阶无穷小量,但特殊情况下要求计算精度必须达到3阶无穷小量,为此目的需要把2阶无穷小平面分成无穷多个4阶无穷小面元来计算通量,并且给出如此计算所得结果遵循的规律——3阶无穷小精度下矢量场穿过2阶无穷小平面的通量定理.最后介绍了这个定理在散度理论和电磁场法向边值关系理论中的应用.