Conformation and internal mobility of 5H-dibenzo[a,d]cycloheptene derivatives in solution. Conformational analysis of highly flexible structures,part II

Summary The conformational possibilities of 5-(3-N,N-dimethylaminopropyl)-5H-dibenzo[a,d]cycloheptene (1), 5-(3-N,N-dimethylaminopropylidene)-10,11-dihydro-5H-dibenzo[a,d]cycloheptene (2), and 5-(3-N,N-dimethylaminopropyl)-10,11-dihydro-5H-dibenzo[a,d]cycloheptene (3) are analysed using empirical force field methods. Minimum energy conformations, interconversion pathways, interconversion graphs and interconversion energies are examined in view of the analysis of conformer equilibria of1,2, or3 in solution. In addition, some basic requirements of the analysis of fast interconverting conformers using the lanthanide induced shift method are discussed.

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Konformation und interne Beweglichkeit von 5H-Dibenzo[a,d]cyclohepten Derivaten in Lösung. Konformationsanalyse hochflexibler Strukturen, Teil 2

Zusammenfassung Die konformativen Möglichkeiten von 5-(3-N,N-dimethylaminopropyl)-5H-dibenzo[a,d]cyclohepten (1), 5-(3-N,N-dimethylaminopropylidene)-10,11-dihydro-5H-dibenzo[a,d]cyclohepten (2) und 5-(3-N,N-dimethylaminopropyl)-10,11-dihydro-5H-dibenzo[a,d]cyclohepten (3) wurden mit Hilfe empirischer Kraftfeldmethoden analysiert. Jene Konformationen, die einem energetischen Minimum entsprechen, sowie Interkonversionswege, Interkonversionsgraphen und Interkonversionsenergien wurden in Hinblick auf die Analyse der Konformerengleichgewichte von1,2 oder3 in Lösung untersucht. Weiters werden noch einige grundlegende Voraussetzungen für die Analyse von sich schnell ineinander umwandelnden Konformeren mittels der Lanthaniden-induzierten Verschiebungsmethode besprochen.

     

Copper Promoted Au/ZnO-CuO Catalysts for Low Temperature Water-gas Shift Reaction

IntroductionThe water-gas shift(WGS)reaction is an impor-tant step in many important chemical processes[1].Re-cently,the renewed interest in the removal of CO bythe WGS reaction has grown significantly because of theincreasing attention to pure hydrogen p…     

部分相干径向偏振拉盖尔-高斯脉冲光束在大气湍流中传输的光谱移动和光谱开关

研究了部分相干径向偏振拉盖尔-高斯(partially coherent radially polarized Laguerre-Gaussian, PCRPLG)脉冲光束在大气湍流中传输时的光谱移动和光谱开关。研究发现,在湍流大气传输时,光束轴上点光谱因受湍流影响产生的双谱峰现象会发生跃变,湍流越强,光谱在跃变后相对谱移变化越稳定,而轴外点光谱在越强的湍流中相对谱移变化范围越小。研究还发现,适当增加脉冲宽度会明显减小大气湍流对光束轴上点和轴外点光谱移动的影响。在不同脉宽下,轴上和轴外点光谱均会出现光谱开关,且轴外点光谱会产生两次光谱跃变的独特现象。在固定的传输距离上,拓扑荷越大,轴上点光谱移动越小,近轴范围内光谱相对谱移的变化范围越小,此外,不同拓扑荷下光谱均会出现谱开关。相干度越大时,光谱的变化越稳定,轴外点光谱的光谱开关发生位置越远。本文的研究结果为多普勒激光雷达的应用提供理 论依据,PCRPLG脉冲光束本身具有较强抗湍流能力,且通过调控光束参数可以减小光束光谱移动。     

组合跳变随机平移宽间隔混沌跳频序列设计

为进一步提高宽间隔跳频序列的性能,基于混沌跳频序列,针对随机平移替代法存在的“窄点”平移与序列平衡性的矛盾问题,提出了一种新的组合跳变随机平移法。该方法在随机平移替代法的基础上取消“窄点”修正,引入组合跳变序列控制频点宽间隔映射。为兼顾组合跳变随机平移法产生序列的平衡性、汉明自相关性和宽间隔特性,构造了跳频序列的复合目标优化函数,引入粒子群算法计算得到最优的序列控制参数。仿真结果表明,组合跳变随机平移法可构造更多的序列,且产生的宽间隔混沌跳频序列具有更好的平衡性、汉明相关性和复杂度,采用粒子群优化获取的控制参数可以实现序列性能的均衡最优。     

基于EMD方法的X波段双偏振雷达衰减订正

针对X波段双偏振雷达信号在降雨路径中的衰减现象,本文提出经验模式分解（Empirical Mode Decomposition,EMD）方法进行X波段双偏振雷达衰减订正,首先对总差分传播相移进行EMD分解得到有限个基本模式分量（Intrinsic Mode Function,IMF）,并基于皮尔逊相关系数准则将IMF分为噪声IMF和信号IMF两类,然后对信号IMF进行有效重构得到差分传播相移,再将差分传播相移通过最小二乘法拟合得到差分传播相移率,最后对求得的差分传播相移与差分传播相移率采用自适应约束方法进行反射率衰减订正。利用EMD方法和其他方法进行对比分析,其结果表明,EMD方法能够有效地消除X波段双偏振雷达回波数据中后向散射的影响,在保留真实的气象信息的同时,有效地抑制差分传播相移的显著波动,进而衰减订正效果更好。     

Oligodeoxyfluorosides: Strong Sequence Dependence of Fluorescence Emission

We describe the properties of a series of oligomeric polyfluorophores assembled on the DNA backbone. The 11 oligomers (oligodeoxyfluorosides, ODFs), 4-7 monomers in length, were composed of only two fluorescent monomers and a spacer in varied sequences, and were designed to test how fluorescent nucleobases can interact electronically to yield complexity in fluorescence emission. The monomer fluorophores were deoxyribosides of pyrene and perylene, which emit light in violet and blue wavelengths, respectively. The experiments show that simple variation in sequence and spacing can dramatically change fluorescence, yielding emission maxima ranging from 380 to 557 nm and visible colors from violet to orange-red. Fluorescence lifetime data, excitation spectra, and absorption data point to a number of multi-fluorophore electronic interactions, including pyrene-pyrene and perylene-perylene excimers, pyrene-perylene exciplexes, as well as monomer dye emissions, contributing to the final spectral outcomes. Thus, two simple fluorophores can be readily combined to give emissions over much of the visible spectrum, all requiring only a single excitation. The results demonstrate that fluorescent nucleobases in oligomeric form can act cooperatively as electronic units, and that fluorophore sequence in such oligomers is as important as fluorophore composition in determining fluorescence properties.     

103Rh-NMR-spektroskopischer Nachweis der gemischten Nonahalogenodirhodate(III), [Rh2ClnBr9–n]3−, n = 0–9

¹⁰³Rh NMR Spectroscopic Evidence of Mixed Nonahalogenodirhodates(III), [Rh₂Cl_nBr_9–n]^3?, n = 0–9 On heating a mixture of the tetrabutylammonium salts (TBA)₃[Rh₂Cl₉] and (TBA)₃[Rh₂Br₉] at 60°C in propylenecarbonate the complete system of the mixed nonahalogenodirhodates(III) [Rh₂Cl_nBr_9–n]^3?, n = 0–9 is formed. In the ¹⁰³Rh nmr spectra 40 different species have been detected, 16 with two equivalent ¹⁰³Rh atoms each resulting in one singlet and 24 with inequivalent ¹⁰³Rh atoms each pair giving two resonances. The signals of the geometric isomeres are not resolved. All 64 expected resonances are really observed. By additional measuring of the ¹⁰³Rh nmr spectra of the fractions n = 0–4 separable by ion exchange chromatography on DEAE cellulose, and utilizing characteristic increments of chemical shifts the complete and unambiguous assignment of all signals is achieved.     

Combined application of 2D NMR correlation methods and ab initio chemical shift calculations to the structure determination of new heterocyclic compounds

The combined use of 2D NMR correlation methods and ab initio chemical shift calculations is efficient and, in some cases, virtually the only way to determine the structures of new organic compounds. This approach enabled us to establish the structure of the major unusual product of the three-component reaction of imidazo[1,5-a]quinoxalin-4-one, bis(2-chloroethyl)amine hydrochloride, and potassium carbonate in DMF. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2172–2179, December, 2006. Dedicated to Professor A. V. Il’yasov on the occasion of his 70th birthday.     

Strategies for measurements of pseudocontact shifts in protein NMR spectroscopy.

Paramagnetic metal ions bound to proteins generate a dipolar field that can be accurately probed by pseudocontact shifts (PCS) displayed by the protein's nuclear spins. PCS are highly useful for determining the coordinates of individual spins in the molecule and for rapid structure determinations of entire protein-protein and protein-ligand complexes. However, PCS measurements require reliable resonance assignments for the molecule in its paramagnetic state and in a diamagnetic reference state. This article discusses different approaches for pairwise resonance assignments, with emphasis on a strategy which exploits chemical exchange between the two states.     

On the origin of quasi-racemic aplysinopsin cycloadducts, (bis)indole alkaloids isolated from scleractinian corals of the family Dendrophylliidae. Involvement of enantiodefective Diels-Alderases or asymmetric induction in artifact processes involving adventitious catalysts?

Reported here are two novel quasi-racemic (bis)indole alkaloids, cycloaplysinopsin A (5) and cycloaplysinopsin B (6), isolated from tropical Indo-Pacific (Comoros, Philippines) scleractinian corals of the family Dendrophylliidae. Although their structures suggest a Diels-Alder cycloaddition origin from aplysinopsin-type precursors, neither experiments, nor theory allowed us to clearly distinguish an enzymatic process with scarce enantioselection from the intrusion of an adventitious catalyst in the coral extracts, where the chiral environment caused a slight asymmetric induction.