异喹啉酰肼构筑锌配合物的合成、晶体结构及其性质

采用普通溶液法合成了配合物[Zn(eiqnthz)_2]·DMF(1)和[Zn3(piqnthz)_2Cl_2]·2H_2O(2)(Heiqnthz=N,N′-乙酰异喹啉甲酰肼,H2piqnthz=N,N′-丙酰异喹啉甲酰肼)。通过X射线单晶衍射分析、X射线粉末衍射分析、红外光谱分析、热重分析以及荧光光谱分析等分析方法对2个配合物进行结构测定和性质表征。结构分析表明配合物1是单核结构,单斜晶系,空间群为C2/c,锌离子周围有4个氮原子和2个氧原子与之配位,形成一个畸变的N4O2八面体构型。配合物2属于单斜晶系,C2/c空间群,三核结构。中心原子Zn(1)、Zn(2)、Zn(3)均为5配位,Zn(1)、Zn(3)位于分子两端并且是变形四角锥配位构型,Zn(2)位于中间形成三角双锥配位构型,整体呈V字型。荧光分析表明Heiqnthz、H2piqnthz与锌(Ⅱ)离子配位后其荧光都发生较大的红移。     

含芴共轭单元的超支化聚合物的合成及表征

以芴和季戊四醇为初始物,分别合成了具有芴共轭单元和季戊四醇多臂结构的两种聚合单体,进一步采用Suzuki反应合成出一种结构新颖的部分共轭结构的超支化聚合物.利用紫外吸收光谱和荧光发射光谱对聚合物予以表征,结果表明,超支化聚合物具有与模型化合物分子相似的发光行为,既可以发出纯正的蓝光,又表现出支化结构对荧光发射的影响.差...     

Efficient asymmetric synthesis of the vasopeptidase inhibitor BMS-189921

[reaction: see text] An efficient asymmetric synthesis of the vasopeptidase inhibitor BMS-189921 was accomplished. Two short enantioselective syntheses of the common key intermediate (S)-alpha-aminoazepinone 6b were developed. Olefin 3 was converted to 6b via asymmetric hydrogenation. Alternatively, enyne 12 was converted to racemic alpha-aminoazepinone 15b, which was transformed to 6b by a practical dynamic resolution.     

Reflection and transmission of waves near the localization threshold

A theory is presented for propagation of waves in bounded media near the mobility edge, based on the self-consistent theory for localization. It predicts a spatially inhomogeneous diffusion constant that leads to scale dependence in enhanced backscattering and transmission.     

Frequency-domain technique for optical property measurements in moderately scattering media

We demonstrate a reflection geometry frequency-domain technique that is suitable for measurement of the optical properties of a medium with moderate scatter and absorption (mu(s) and mu(a) ~ 1 m(-1)). Variations in absorption and scatter produce opposing tends in the amplitude signal and common trends in the phase signal, allowing unique determination of absorption and scattering coefficients for a given phase function. An analytical model based on single-scattering events gives good agreement with experimental measurements.     

两种气液两相流模型的应用和比较

本文应用MUSIG模型[1]和均一直径模型对某溶液堆台架模型堆芯内气液流动传热进行了数值模拟.在MUSIG模型中堆芯内离散相气泡被分为5组不同直径的气泡,用于分析堆芯内气泡的流动变化和大小分布,采用Luo and Svendsen[2]和Prince and Blanch[3]模型描述不同直径气泡组间的破裂和聚合.在均一直径模型中,堆芯内的气体被考虑为同一直径的组分,并且不考虑其破裂与聚合现象.计算得到采用两个模型的模拟结果并且对其进行了对比研究.结果显示应用MUSIG模型的计算结果与台架实验结果吻合更好.     

Six-Fold Degenerate Dark States in a Four-Level Atomic System

With all driving fields on Raman resonance, a tripod-type atomic system quickly evolves into a dark state decoupled from the lossy excited level. The dark state depends strongly on field Rabi frequencies, spontaneous decay rates, and the initial atomic population in a complicated way. Analytical results reveal that it is a sixfold degenerate dark state with its three components superposed both coherently and incoherently due to population redistribution from spontaneous emission.     

Investigation of uremic analytes in hemodialysate and their structural elucidation from accurate mass maps generated by a multi‐dimensional liquid chromatography/mass spectrometry approach

Historically, structural elucidation of unknown analytes by mass spectrometry alone has involved tandem mass spectrometry experiments using electron ionization. Most target molecules for bioanalysis in the metabolome are unsuitable for detection by this previous methodology. Recent publications have used high‐resolution accurate mass analysis using an LTQ‐Orbitrap with the more modern approach of electrospray ionization to identify new metabolites of known metabolic pathways. We have investigated the use of this methodology to build accurate mass fragmentation maps for the structural elucidation of unknown compounds. This has included the development and validation of a novel multi‐dimensional LC/MS/MS methodology to identify known uremic analytes in a clinical hemodialysate sample. Good inter‐ and intra‐day reproducibility of both chromatographic stages with a high degree of mass accuracy and precision was achieved with the multi‐dimensional liquid chromatography/tandem mass spectrometry (LC/MS/MS) system. Fragmentation maps were generated most successfully using collision‐induced dissociation (CID) as, unlike high‐energy CID (HCD), ions formed by this technique could be fragmented further. Structural elucidation is more challenging for large analytes >270 Da and distinguishing between isomers where their initial fragmentation pattern is insufficiently different. For small molecules (<200 Da), where fragmentation data may be obtained without loss of signal intensity, complete structures can be proposed from just the accurate mass fragmentation data. This methodology has led to the discovery of a selection of known uremic analytes and two completely novel moieties with chemical structural assignments made. Copyright © 2009 John Wiley & Sons, Ltd.     

Accurate mass measurement: Terminology and treatment of data

High-resolution mass spectrometry has become ever more accessible with improvements in instrumentation, such as modern FT-ICR and Orbitrap mass spectrometers. This has resulted in an increase in the number of articles submitted for publication quoting accurate mass data. There is a plethora of terms related to accurate mass analysis that are in current usage, many employed incorrectly or inconsistently. This article is based on a set of notes prepared by the authors for research students and staff in our laboratories as a guide to the correct terminology and basic statistical procedures to apply in relation to mass measurement, particularly for accurate mass measurement. It elaborates on the editorial by Gross in 1994 regarding the use of accurate masses for structure confirmation [1]. We have presented and defined the main terms in use with reference to the International Union of Pure and Applied Chemistry (IUPAC) recommendations for nomenclature and symbolism for mass spectrometry. The correct use of statistics and treatment of data is illustrated as a guide to new and existing mass spectrometry users with a series of examples as well as statistical methods to compare different experimental methods and datasets.     

堆焊熔敷层表面纳米晶层摩擦磨损性能研究

用预压力滚压技术在堆焊修复层表面制备纳米晶层.利用TEM、SEM分析技术研究表面纳米晶层微观结构,利用CETR-3型多功能摩擦磨损试验机考察在干摩擦条件下堆焊层表面纳米晶层的摩擦磨损性能.结果表明堆焊修复层表面经表面纳米化处理后,表面形成厚度约为10μm(晶粒尺寸小于100 nm)的纳米晶层,最表面层平均晶粒尺寸约为10 nm.纳米压痕试验表明纳米晶层的硬度提高,最表面纳米晶层的硬度约为原始堆焊层硬度的3倍.与原始堆焊试样相比,表面纳米化试样的摩擦系数降低了10%,磨损体积降低了25%~30%左右.表面纳米化样品的磨损机制由原始堆焊层的磨粒磨损和黏着磨损转变为磨粒磨损,分析表明晶粒细化导致的高硬度、低塑性是摩擦磨损性能改善和磨损机制改变的主要原因.