扶手椅型单壁碳纳米管氮烯环加成异构体结构和性质的理论研究

用AM1方法研究了(3，3)、(4，4)、(5，5)和(6，6)扶手椅型单壁碳纳米管(ASWCNTs)以及其氮烯环加成异构体的结构和性质，并重点讨论了这些异构体之间的转化关系．POAV分析表明，扶手椅型单壁碳纳米管的直径越大，张力就越小，“一“共轭作用也越强．     

有机化学教学研究2例

对如下两个有机化学教学问题进行了探讨:(1)如何确定链状多烯顺反异构体的数目和类型;(2)单糖的Fischer投影式转变为透视式的简便方法。     

ω-9-蒽多亚甲基羧酸-甲基取代香豆素酯的合成及其光性能研究

合成了9个新的双荧光团化合物ω-9-蒽多亚甲基羧酸-甲基取代香豆素酯和3个模型化合物,讨论了这些化合物的结构与光性能之间的关系。     

薄层色谱法分离烷基芳基酮肟立体异构体

我们对酮肟中间体及肟醚类拟除虫菊酯进行了分析。经核磁共振证明,酮肟中间体在生成肟醚南反应过程中其立体构型木发生变化。目前分离酮肟立体异构物的工作报道较少。我们通过薄层色谱对不同取代的具有活性的几种酮肟异构体的分离进行了探讨。 1 实验部分     

Determination of toluenesulfonic acid isomers by gas chromatography

Summary A gas chromatographic method for the determination of isomeric distribution in toluenesulfonic acid samples is described. The acids are transformed into the corresponding ethyl esters by reaction with triethyl orthoformate in toluene. The reaction mixture can be injected, without further purification, into the gas chromatograph. The separation is best performed on columns containing OV-210 or polyphenyl ether (6 rings) as the stationary phase.     

Improving Our Knowledge on the 229mThorium Isomer: Toward a Test Bench for Time Variations of Fundamental Constants

For more than four decades, the lowest excitation in the whole landscape of atomic nuclei, the low‐lying, isomeric state of ²²⁹Th, the so‐called thorium isomer, has challenged physicists of various disciplines. Being a solitaire with its uniquely low excitation energy of <10 eV, its predicted lifetime of a few hours results in an extremely sharp relative linewidth ΔE/E as low as 10^–20. While until recently the indication of its existence was based only on indirect evidence, its unique properties inspired a multitude of potential applications, like the use of the thorium isomer as a nuclear frequency standard, potentially able to outperform even the best atomic clocks and a sensitivity‐enhanced access to potential temporal variations of fundamental constants. The various proposals to exploit the unique properties of ^229mTh are presented herein, in particular focusing on its ability to serve as a test bench for time variations of fundamental constants like the fine structure constant.     

Mechanism of UV-induced formation of Dewar lesions in DNA

The importance of a backbone: The mechanism of formation of Dewar lesions has been investigated by using femtosecond IR spectroscopy and ab?initio calculations of the exited state. The 4π?electrocyclization is rather slow, occurs with an unusual high quantum yield, and--surprisingly--is controlled by the phosphate backbone.     

Is Quantum Tunneling Relevant in Free‐Radical Polymerization?

Quantum tunneling in hydrogen transfer reactions active in FRP is investigated theoretically. Three systems are examined: polyethylene, polystyrene, and poly(vinyl chloride). Kinetic parameters of backbiting reactions are evaluated adopting quantum chemistry. Tunneling corrections are estimated adopting the one‐dimensional Eckart model, which provides a reasonable accuracy along with a limited computational effort. The relevance of quantum tunneling in the investigated systems is highlighted, with focus on the temperature dependence of the tunneling correction in the typical polymerization conditions of the investigated monomers. Obtained results clearly show that tunneling plays an important role in the kinetics estimation of hydrogen abstractions in FRP.

     

麻黄生物碱中一对光学异构体在薄层色谱原位的表面增强拉曼光谱研究

应用表面增强技术(SERS)将薄层色谱(TLC)与傅里叶变换拉曼光谱(FT-Raman)联用,在薄层色谱分离斑点原位,获得中草药麻黄中麻黄生物碱衍生物中一对关于手性碳的光学异构体：去甲基麻黄碱,去甲基伪麻黄碱指纹光谱的新方法。研究表明,在薄层色谱原位仅16 μg的样品,就可获得以上分子的主要特征谱带;并且光学异构体的光谱特征明显不同,在银溶胶微粒表面增强作用下去甲基麻黄碱、去甲基伪麻黄碱分子中与苯环相关的波数为1 004,1 605 cm-1振动获最大增强。从而阐明了应用TLC-SERS联用技术,可有效地对中草药主要化学成分中光学异构体进行高灵敏度分离与指纹鉴定。     

Searching for high-K isomers in the proton-rich A～80 mass region

Configuration-constrained potential-energy-surface calculations have been performed to investigate the K isomerism in the proton-rich A～ 80 mass region. An abundance of high-K states are predicted. These high-K states arise from two and four-quasi-particle excitations, with K~π= 8~+ and K~π= 16~+, respectively. Their excitation energies are comparatively low, making them good candidates for long-lived isomers. Since most nuclei under study are prolate spheroids in their ground states, the oblate shapes of the predicted high-K states may indicate a combination of K isomerism and shape isomerism.