国内气相色谱近年的进展

本文对近三年国内学者在气相色谱方面的研究和应用作了综述 ,国内学者的研究基本和国际上气相色谱方面的研究类似 ,在全二维气相色谱、快速气相色谱 ,微型气相色谱仪、新型气相色谱固定相和色谱柱的溶胶 凝胶涂渍技术领域的研究方面作出了贡献。有关气相色谱的应用研究中 ,介绍了大量在药物分析、食品分析、环境分析、石油和石化分析和化工产品及高聚物分析等领域中应用的题目和摘要     

A consecutive one-pot two-step approach to novel trifluoromethyl-substituted bis(indolyl)methane derivatives promoted by Sc(OTf)3 and p-TSA

A one-pot two-step reaction of 3-(trifluoroacetyl)coumarin and indole afforded trifluoromethyl-substituted bis(indolyl)methane compounds containing coumarin skeleton. The atomic economic and simply manipulative reaction involved premier treatment of reaction mixtures with Sc(OTf)₃, followed by p-TSA in one-pot process. The reaction proceeded to give the title compounds in high yields (up to 95% yield).     

Highly stereoselective synthesis of (Z)-3-methoxy-1-methyleneisoindoles via DMAP catalyzed cyclization of methyl 2-alkynylbenzimidates

A DMAP (4-dimethylaminopyridine) catalyzed cyclization of methyl 2-alkynylbenzimidates has been developed, which affords 3-methoxy-1-methyleneisoindoles with excellent Z-stereoselectivity under mild and transition-metal-free conditions. The (Z)-3-methoxy-1-methyleneisoindole products can be converted to corresponding 3-amino-1-methyleneisoindoles, 3-methoxy-isoindoles, 3-methyleneisoindolinones and isoindolinones with high efficiency.     

Polymerizable C70 derivatives with acrylate functionality for efficient and stable solar cells

Fullerene-based organic solar cells are generally suffering from severe microstructure evolution occurring in their bulk heterojunction active layers and thus are extremely stable. To address it, four polymerizable C₇₀ fullerene derivatives, [6,6]-phenyl-C₇₁-ethyl acrylate (PC₇₁EA), [6,6]-phenyl-C₇₁-propyl acrylate (PC₇₁PrA), [6,6]-phenyl-C₇₁-butyl acrylate (PC₇₁BA), and [6,6]-phenyl-C₇₁-pentyl acrylate (PC₇₁PeA), have been designed, synthesized, and investigated. These fullerene compounds have a molecular structure, shape and size very like the conventional C₇₀ fullerene acceptor, [6,6]-phenyl-C₇₁-butyric acid methyl ester (PC₇₁BM), and have been found no different in their light absorption, redox potentials, and frontier orbital energy levels. Using these fullerene acrylates individually as acceptor and poly(3-hexylthiophene) as donor, organic solar cells have been fabricated and gave optimal efficiencies ranging from 3.32% to 4.16%, comparable to PC₇₁BM-based reference cells (4.06%). Owing to their acrylate functionality, these fullerene derivatives can turn into insoluble upon heating, and thus endow their solar cell devices much better thermostability than PC₇₁BM-based reference cells. The best one, coming from PC₇₁PeA devices, reported an optimal efficiency of 4.16%, and maintained 91.7% efficiency after heat treatment at 150 °C for 35 h. As a sharp contrast, the PC₇₁BM reference cell dropped its optimal efficiency from 4.06% to 0.48% only after 5 h heat treatment. X-ray diffraction, optical and atomic force microscopy, and space-charge-limited current method have been carried out to understand active layer structure, morphology, and charge mobility change during heat treatment.     

Erythrina alkaloids from leaves of Erythrina arborescens

Continued interest in Erythrina alkaloids resulted in the isolation of 38 alkaloids including 7 undescribed ones from the leaves of Erythrina arborescens Roxburgh. Among the new compounds, erythrivarines H-I were two dimeric alkaloids, while others were Erythrina alkaloid glucosides. Dimeric Erythrina alkaloids and monomers, turcomanidine and isoboldine, showed medium xanthine oxidase inhibition.     

Copper-catalyzed aryldifluoromethylenation of N-arylacrylamides to synthesis of the diheterocyclic compounds linked by gem-difluoromethylene moiety

An efficient method of copper-catalyzed aryldifluoromethylenation of N-arylacrylamides is described to step-economic synthesis of the various biologically important biheterocyclic compounds linked by gem-difluoromethylene moiety through addition of benzo-1,3-azolic (oxa- or thia-)difluoromethyl radicals generated in situ to terminal of C–C double bond of N-arylacrylamides then cyclization cascade. This protocol has demonstrated to have broad substrate scope and excellent functional-group tolerance under mild reaction conditions.     

Three new dibromopyrrole alkaloids from the South China Sea sponge Agelas nemoechinata

Three new dibromopyrrole alkaloids, 9-N-methylcylindradine A (1), 1-N-methylugibohlin (2), nemoechine H (3), together with one known dibromopyrrole alkaloid N-methyldibromoisophakellin (4) were isolated from the South China Sea sponge Agelas nemoechinata. Their structures were elucidated by comprehensive spectroscopic methods including HRESIMS and NMR, and the absolute configuration of compound 1 was further confirmed by comparison of optical rotation. Compound 3 exhibited moderate cytotoxic activity against K562 and L-02 with IC₅₀ values of 6.1 μM and 12.3 μM, respectively.     

南海IODP 349航次U1434站位海相红层成因——来自漫反射光谱与X荧光光谱的制约

提出IODP349航次首次在南海发现的大洋红层,与ODP124 航次苏禄海、苏拉威西海大洋红层以及三水盆地陆相红层相似,都具有直接覆盖于大规模岩浆岩之上的特征,对于揭示红层与岩浆热事件的关系具有重要意义。自上而下采集U1434站位灰绿色-红棕色海相沉积序列进行测试分析,并设计实验模拟沉积-成岩过程中氧逸度和地热温度对红层色素形成的控制作用,通过红色与非红色沉积、实测与实验样品的对比分析,探讨红层成因机制及其地质意义。采用漫反射光谱、荧光光谱分析以及二价铁滴定测试,量化分析了海相沉积与实验样品的颜色红度值、针铁矿、赤铁矿与不同价位铁元素的含量,得到以下新认识：U1434站位红色-非红色海相沉积均形成于较高的氧逸度条件,水体氧化还原环境的差异并不是控制红色与非红色沉积的主要因素;U1434站位大洋红层直接覆盖大洋玄武岩,起源于沉积-成岩阶段的高地温作用;陆相红层和白垩纪海相红层均分布于相应时期的构造-岩浆活动带,暗示了红层对地质热事件具有重要的指示意义。     

Acoustic absorbers at low frequency based on split-tube metamaterials

The remarkable properties of acoustic metamaterials have attracted massive researches and applications, especially on low-frequency sound absorptions. Currently, most of the acoustic metamaterial absorbers employ resonances in plastic cavities, and their structural strengths are important in many circumstances, especially in harsh environment. However, studies of metamaterials including this point are very scarce. Here, we propose an acoustic metamaterial for low-frequency (<500 Hz) absorptions, composed of three nested square split tubes with inverted opening directions. The efficiency of the absorber is investigated both numerically and experimentally, and absorptions at the peeks are found to exceed 90% and the frequency can be effectively adjusted by tuning its geometric parameters. We further test its yield strength under compression and confirm its buckling behavior happens from the outmost layer. This tunable acoustic metamaterial with a fairly good mechanical strength may lead to broad applications in noise reduction.     

Self-assembly of l-tryptophan on Cu(111) studied by low-temperature scanning tunneling microscopy

The self-assembly of l-tryptophan on Cu(111) is investigated by an ultrahigh vacuum scanning tunneling microscope (STM) at 4.4 K. When deposited onto the substrate at around 120 K with a coverage of 0.1 monolayer, molecular trimers, tetramers, hexamers, and chains coexist on Cu(111). Then almost all molecules self-assemble into chiral hexamers after being annealed at room temperature. When increasing molecular coverage to the full layer, a new type of chain is observed on the surface. Based on the high-resolution STM images at sub-molecular level, we suggest that the l-tryptophan molecules are present in neutral, zwitterionic or anionic states in these structures.