环加成反应、环合反应、电环化反应与环化反应的区别*

环加成反应、环合反应、电环化反应与环化反应都是合成有机环状化合物的成环反应,它们描述的反应类型完全不同。但是,它们却经常被误用或者混用。阐述了这4类反应的区别,希望能够从教学上明确这4类反应,从源头为将来的有机化学工作者建立起准确的概念。     

Assessment of a high‐order MUSCL method for rotor flows

This work presents the implementation of a high‐order, finite‐volume scheme suitable for rotor flows. The formulation is based on the variable extrapolation MUSCL‐scheme, where high‐order spatial accuracy (up to fourth‐order) is achieved using correction terms obtained through successive differentiation. A variety of results are presented, including 2‐ and 3‐dimensional test cases. Results with the proposed scheme, showed better wake and higher resolution of vortical structures compared with the standard MUSCL, even when coarse meshes were employed. The method was also demonstrated for 3‐dimensional unsteady flows using overset and moving grids for the UH‐60A rotor in forward flight and the Enhanced Rotorcraft Innovative Concept Achievement tiltrotor in aeroplane mode. For medium grids, the present method adds reasonable CPU and memory overheads and offers good accuracy on relatively coarse grids.     

Sequencing and characterisation of complete mitogenome DNA for Rasbora sarawakensis (Cypriniformes: Cyprinidae: Rasbora) with phylogenetic consideration

The Blueline Rasbora (Rasbora sarawakensis) is a small ray-finned fish categorized under the genus Rasbora in the Cyprinidae family. In this study, the complete mitogenome sequence of R. sarawakensis was sequenced using four primers targeting overlapping regions. The mitogenome is 16,709 bp in size, accommodating 22 transfer RNA genes, 13 protein-coding genes, two ribosomal RNA genes and a putative control region. Identical gene organisation was detected between this species and other genus counterparts. The heavy strand houses 28 genes while the light strand stores the other nine genes. Most protein-coding genes employ ATG as start codon, excluding COI gene, which utilizes GTG instead. The central conserved sequence blocks (CSB-F, CSB-E and CSB-D), variable sequence blocks (CSB-3, CSB-2 and CSB-1) as well as the terminal associated sequence (TAS) are conserved in the control region. The maximum likelihood phylogenetic tree revealed the divergence of R. sarawakensis from the basal region of the Rasbora clade, where its evolutionary relationships with R. maculatus and R. pauciperforata are poorly resolved as indicated by the low bootstrap values. This work acts as steppingstone towards further molecular evolution and population genetics studies of Rasbora genus in future.     

西北太平洋表层沉积物地球化学特征及其物源指示意义

为深入了解西北太平洋表层沉积物地球化学特征及物质来源，对大洋40航次在西北太平洋马尔库斯-威克海山区采集的表层沉积物进行了全岩地球化学和黏土矿物测试分析。结果表明，研究区表层沉积物稀土元素（REE)平均质量分数为302.87×10^-6，北美页岩标准化稀土配分模式与黄土相似，并具Ce轻微负异常和Eu无异常特征。稀土配分模式、判别函数（discriminant functions,DF）、M/I（蒙脱石/伊利石）及涂片鉴定等结果指示沉积物物源具有多源性，主要为陆源风尘物质，并受海洋自生物质的强烈影响，海山玄武岩及其蚀变产物和硅质生物也有一定的贡献。研究区沉积物稀土特征既不同于边缘海沉积物，也有别于远洋沉积物，而与弧后盆地沉积物类似。结合1/δCe-LREE/HREE和LREE/HREE-Y/Ho判别图解结果，研究区沉积物物源结构属性应介于边缘海沉积物与远洋沉积物之间，为洋陆过渡区沉积。     

Electrical Stimulation of Human Mesenchymal Stem Cells on Conductive Substrates Promotes Neural Priming

Electrical stimulation (ES) within a conductive scaffold is potentially beneficial in encouraging the differentiation of stem cells toward a neuronal phenotype. To improve stem cell-based regenerative therapies, it is essential to use electroconductive scaffolds with appropriate stiffnesses to regulate the amount and location of ES delivery. Herein, biodegradable electroconductive substrates with different stiffnesses are fabricated from chitosan-grafted-polyaniline (CS-g-PANI) copolymers. Human mesenchymal stem cells (hMSCs) cultured on soft conductive scaffolds show a morphological change with significant filopodial elongation after electrically stimulated culture along with upregulation of neuronal markers and downregulation of glial markers. Compared to stiff conductive scaffolds and non-conductive CS scaffolds, soft conductive CS-g-PANI scaffolds promote increased expression of microtubule-associated protein 2 (MAP2) and neurofilament heavy chain (NF-H) after application of ES. At the same time, there is a decrease in the expression of the glial markers glial fibrillary acidic protein (GFAP) and vimentin after ES. Furthermore, the elevation of intracellular calcium [Ca²⁺] during spontaneous, cell-generated Ca²⁺ transients further suggests that electric field stimulation of hMSCs cultured on conductive substrates can promote a neural-like phenotype. The findings suggest that the combination of the soft conductive CS-g-PANI substrate and ES is a promising new tool for enhancing neuronal tissue engineering outcomes.     

Pretreating near infrared spectra with fractional order Savitzky–Golay differentiation(FOSGD)

With the aid of Riemann–Liouville fractional calculus theory,fractional order Savitzky–Golay differentiation(FOSGD) is calculated and applied to pretreat near infrared(NIR) spectra in order to improve the performance of multivariate calibrations.Similar to integral order Savitzky–Golay differentiation(IOSGD),FOSGD is obtained by fitting a spectral curve in a moving window with a polynomial function to estimate its coefficients and then carrying out the weighted average of the spectral curve in the window with the coefficients.Three NIR datasets including diesel,wheat and corn datasets were utilized to test this method.The results showed that FOSGD,which is easy to compute,is a general method to obtain Savitzky–Golay smoothing,fractional order and integral order differentiations.Fractional order differentiation computation to the NIR spectra often improves the performance of the PLS model with smaller RMSECV and RMSEP than integral order ones,especially for physical properties of interest,such as density,cetane number and hardness.     

Solubility of tridecanedioic acid in pure solvent systems: An experimental and computational study

Solubility has been extensively investigated by the phase equilibria approach at the mesoscale level, but its origin on the molecular and electronic levels is poorly understood. This study explored the solubility behaviour of crystalline solid in selected pure solvents with various functional groups by using both phase equilibria and molecular modelling methods. The model compound tridecanedioic acid (TDDA) solubility in methanol, ethanol, acetic acid, acetone, and ethyl acetate was determined from T = (283.15 to 323.15) K by a static method. It was found that almost all solutions studied exhibit non-ideal behaviour and deviate positively from Raoult’s law indicating the important role of homo-molecules interactions. Thermodynamic analyses of solution suggest that both enthalpy and entropy of solution govern the dissolution process. Computational studies on solubility behaviour were performed by using both density functional theory (DFT) calculations and molecular dynamic (MD) simulations. The results conclude that the (solute + solvent) interaction is not the only factor determining solubility, and (solvent + solvent) interaction also plays an important role. The simulated results are found to be qualitatively consistent with experimental values. Finally, solubility values were correlated by the empirically modified Apelblat equation and two local composition models of Wilson and NRTL.     

回归知识本原 构建生命课堂——以“常见物质的检验”为例

以“常见物质的检验”的教学为例,运用化学史料帮助学生自主建构知识体系,促进学生追寻知识本原,实现思维进阶,发展核心素养,并阐述运用化学史料构建高中化学生命课堂的实施策略。     

矿物元素指纹图谱的建立及在西洋参产地鉴别中的应用研究

采用电感耦合等离子体质谱法测定了山东、吉林、美国和加拿大4个产地西洋参中50种矿物元素的含量,研究了不同产地西洋参矿物元素的差别和转换系数,构建了西洋参的矿物元素指纹图谱。以各产地矿物元素含量的平均值构建了山东、吉林、美国和加拿大产西洋参的矿物元素标准指纹图谱。采用SPSS 20.0计算了各西洋参矿物元素指纹图谱与其矿物元素标准指纹图谱的相似度,确定了山东、吉林、美国和加拿大产西洋参矿物元素指纹图谱的相似度阈值分别为0.93、0.91、0.98和0.93。通过比较未知产地西洋参矿物元素指纹图谱与矿物元素标准指纹图谱的相似度,进行西洋参的产地判别。采用20批未知产地西洋参样品验证模型的准确性,正确率为85%。此外,研究表明,不同生长年限和不同部位西洋参样品对所建立的西洋参产地鉴别方法无影响。     

基于质子转移反应-飞行时间质谱快速鉴别不同产地闽北水仙茶

采用质子转移反应-飞行时间质谱仪(PTR-TOF-MS), 构建了3个产地(武夷山、建阳、建瓯)113个闽北水仙茶样品香气的化学指纹图谱, 对所得的闽北水仙茶香气指纹图谱进行主成分分析(PCA), 获得了不同产地闽北水仙茶样品的质谱信息特征, 然后采用软独立建模分类法(SIMCA)、K最邻近结点算法(KNN)、偏最小二乘判别分析法(PLS-DA)对闽北水仙茶的质谱信息进行了模式识别.结果表明, PTR-TOF-MS结合分类识别模式能有效区分不同产地的闽北水仙茶.PCA 提取了3个主成分, 累计贡献率为84.66%;3个识别模型的校正集判别正确率分别为89.38%、100.00%和100.00%, 预测集的判别正确率分别为83.18%、 96.46%和95.57%.基于此成功建立了不同产地的闽北水仙茶识别模型.本方法无需样品预处理、分析速度快、灵敏度高、对茶叶无损伤, 为茶叶产地溯源提供了新方法.