近期热点文章北大核心CSCD

关键词：Na＋活性·化学电源Operando研究方法Q. Li, Z. Liu, F. Zheng, R. Liu, J. Lee, G. Xu, G.Zhong, X. Hou, R. Fu, Z. Chen, K. Amine, J. Mi, S.Wu, C. P. Grey, Y. Yang. Identifying the Structural Evolution of the Na-Ion Battery Na2Fe PO4F Cathode,Angew. Chem. Int. Ed., 10.1002/anie.201805555.厦门大学杨勇教授和合作者采用原位高能XRD、固态NMR和DFT理论方法,研究了Na2FePO4F阴极材料循环过程中晶体结构的动态变化,发现存在两种Na＋晶格位点,但只有一种有电化学活性.化学电源中的Operando研究方法为揭示电极活性物质的构效关系和反应机理提供了有力工具.     

勘误

倪哲明,夏明玉,施炜,钱萍萍.糠醛在Pt(111)表面的吸附和脱碳反应.物理化学学报,2013,29(9),1916,论文的中文题目"糠醛在Pt(111)表面的吸附和脱碳反应"改为"糠醛在Pt(111)表面的吸附和脱羰反应".TOC和文章图5中糠醛的化学结构改为.NI Zhe-Ming,XIA Ming-Yu,SHI Wei,QIAN Ping-Ping.Adsorption and Decarbonylation Reaction of Furfural on Pt(111)Surface.Acta Phys.-Chim.Sin.2013,29(9),1916,the Chinese title"糠醛在Pt(111)表面的吸附和脱碳反应"should be"糠醛在Pt(111)表面的吸附和脱羰反应",and the chemical structure of furfural in TOC figure and Fig.5 should be.     

H-ZSM-5催化甲苯与碳酸二甲酯和甲醇甲基化的反应机理

对二甲苯是重要的石油化工产品之一, 可以通过甲苯甲基化生产. 本文采用“our own-N-layeredintegrated molecular orbital+molecular mechanics”(ONIOM)和密度泛函理论(DFT)结合的方法, 计算了H-ZSM-5催化甲苯与碳酸二甲酯(DMC)和甲醇甲基化反应机理. 考察了反应物吸附和产物脱附. 描述了主要的中间物种和过渡态的结构. 用计算的速率常数来估计甲苯甲基化反应的动力学活性. H-ZSM-5 催化的甲苯与DMC和甲醇甲基化的机理不同. 甲苯和DMC甲基化包括DMC完全解离, 接着甲基化生成二甲苯异构体. 相比而言, 在甲苯甲基化反应中, 甲醇作为甲基化试剂的活性比DMC更好. 甲苯和甲醇甲基化的分步反应路径和联合反应路径的本征活化能相似. 在773 K, 分步反应路径的速率常数比联合反应路径更高. 在甲苯和这两种试剂甲基化的反应中, 生成对二甲苯为动力学优先, 而间二甲苯为能量最低产物. 我们的计算结果和实验观察到的现象一致.     

《锂电池和锂离子电池中的电解质》

2014年秋,Springer出版社刊印了《Modern Aspects of Electrochemistry》系列丛书的第58卷,书名为《Electrolytes for Lithium and Lithium-Ion Batteries》（锂电池和锂离子电池中的电解质）. 该书由美国军队研究实验室（U.S. Army Research Laboratory）的三位科学家T. Richard Jow, Kang Xu, Oleg Borodin 及日本三菱化学株式会社（Mitsubishi Chemical Corporation）的Makoto Ue 共同担任本卷编辑. 知名电化学家J. O’M. Bockris和B. E. Conway在上世纪50年代初共同主编了《Modern Aspects of Electrochemistry》的第一卷,并由美国学术出版社（Academic Press）于1954年出版. 2006年之后,Bockris和 Conway二位先驱因年事已高而不再参与丛书编辑工作. 目前的丛书主编为R. E. White和C. G. Vayenas. 《锂电池和锂离子电池中的电解质》一书对锂电池和锂离子电池中所使用的电解质的种类、特性及所涉及的研究方法和理论问题进行了详尽的讨论,不仅引述了相关领域的近几年重要文献,还对此进行了有独特见地的评述,颇有参考价值. 近年来所出版的与锂电池及锂离子电池相关的中英文书籍种类繁多,但专门论述电池中所用电解质的书籍却极为少见. 特此向本刊读者推荐和作一简略评介.     

仿贝壳结构的自组装有机-无机纳米复合薄膜的制备及结构表征

利用超分子自组装法在玻璃表面制备了聚合前后 DMTB/Si O2 和 DMCB/Si O2 复合薄膜 .在所制备的复合薄膜中 ,表面活性剂 DMTB和 DMCB既作结构导向剂 ,又作聚合单体 .用 FTIR,XRD和 TEM等表征了薄膜的结构 .结果表明 ,所制备的薄膜具有有机 -无机有序交替的层状结构 .DMCB/Si O2 和 DMTB/Si O2复合薄膜有机层与无机层间的距离分别为聚合前 3 .48和 3 .44nm,聚合后 2 .84和 2 .92 nm.     

四氯合金属(II)酸烷铵在280-500K间的热力学性质和相变 I:四氯合锰(II)酸n-十二烷铵

在280-500K的温度范围内用自动绝热量计测定了(n-C12HxNH3)2MnCl4的热容.发现了两个固-固相变,固ID→固II和固I→固II.前者的相变温度、相变焓和相变熵分别为330.6±0.1K,47.78±0.29kJ.mol^-^1和144.5±0.9J.K^-^1.mol^_^1,后者的对应相变热参数分别为334.5±0.1K,5.96±0.05kJ.mol^-^1和17.82±0.15J.K^-^1.mol^-^1.报道了该物质每隔10K的热力学性质.     

超声提取/超高效液相色谱-串联质谱法测定土壤中乙酰甲胺磷与甲胺磷的研究

建立了超声提取/超高效液相色谱-三重四极杆串联质谱(UPLC-MS/MS)快速测定土壤中乙酰甲胺磷和甲胺磷的方法。10. 0 g土壤样品采用20. 0 m L甲醇超声萃取30 min,取上清液过0. 22μm滤膜后进行UPLC-MS/MS分析,外标法定量。结果表明:乙酰甲胺磷和甲胺磷在0. 002～20. 0μg/L质量浓度范围内线性良好(r~2 0. 999),方法检出限分别为0. 004 9μg/kg和0. 003 4μg/kg。在0. 400、4. 00、40. 00μg/kg加标水平下,土壤样品中乙酰甲胺磷和甲胺磷的平均回收率分别为83. 0%～91. 5%和88. 0%～94. 8%,相对标准偏差(RSD,n=6)分别为2. 3%～4. 8%和1. 8%～4. 2%。该方法前处理简单快捷、灵敏度高、定性定量准确,可用于土壤样品中乙酰甲胺磷和甲胺磷含量的快速检测。     

壳聚糖微图形的制备及表征

通过微转移模塑法, 在硅片表面制备了圆形点阵、 方形点阵、 沟槽和波浪等4种形貌的壳聚糖(CS)微图形. CS微图形清晰规整, 成型效果良好. 成骨细胞在圆形点阵和方形点阵上借助伪足多攀附于点阵凸起处. 点阵图形对细胞增殖和分化无影响. 在沟槽和波浪微图形中, 成骨细胞大多被限制在沟区, 且沿着沟槽方向伸展. 沟槽和波浪微图形不利于细胞分化, 但能促进细胞增殖.     

人工神经网络光致发光法同时测定α-萘乙酸和吲哚-3-乙酸

研究了酸度、有机溶剂、重原子效应和共存物对α-萘乙酸(NAA)及吲哚-3-乙酸(IAA)光致发光性质的影响,建立了人工神经网络不经分离同时测定NAA和IAA的新方法。该法测定NAA和IAA的线性范围分别是0.012~0.24 mg.L-1和0.0034~0.068 mg.L-1(荧光)0、.18~1.8 mg.L-1和0.18~1.8 mg.L-1(燐光),检出限分别为0.0039 mg.L-1和0.0019 mg.L-1(荧光)0、.14 mg.L-1和0.13 mg.L-1(燐光)。方法用于合成样和水样测定,回收率在93%~109%之间,结果满意。     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.