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.     

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。     

北京市朝阳区食品污染物监测状况分析

为通过2008年北京市朝阳区食品污染物监测,了解辖区部分食品铅、镉、铝的污染现状,给食品风险评估和政府部门强化监管提供依据,按照国家标准方法GB／T5009对13种135件食品样品进行了铅、镉、铝含量的监测。结果表明,100件样品中铅超标率为6．O％,镉超标率为0;35件样品铝的超标率为65．71％。显示辖区经销的食品中重金属确有污染存在,而铝在油炸面制品和天然海蜇中超标率较高,仍对人体健康存在威胁。     

四川泸定县泥石流灾害成因、特征与防治建议

泸定县地处川西高原与四川盆地的过渡地带,地质环境条件复杂,分布泥石流沟127条,发育密度054条·10km-2。在遥感解译和地面调查基础上,论述了泸定县泥石流灾害成因、发生特征、危害和发展趋势,提出了相关防治建议。(1)成因表现为复杂的断裂构造导致流域内松散物源丰富,较大的相对高差提供了良好势能条件,而汛期集中强降雨则提供了动能条件,且雨量条件中当日雨量与前期有效降雨量之间具有幂函数关系; (2)发生特征表现出典型的空间群发性(包括2005-06-30群发性泥石流、2005-08-11群发性泥石流和2006-07-14群发性泥石流)与时间的夜发性; (3)危害方式主要包括淤埋、冲毁、侵蚀、堵河4种,泥石流已造成74人死亡; (4)发展趋势表现为泥石流沟多处于形成期和发展期(113条,占89%),发生的年际准周期由20a缩短至不足10a,且发生条(次)由4条(次)增加至44条次(2005年); (5)泸定县泥石流防治的突出问题表现为城镇泥石流问题、泥石流堵塞主河问题、风景区泥石流问题与冲沟泥石流问题,建议通过科学规划、风险防御体系构建、土木工程治理、监测预警等措施予以防御。     

Synthesis of isoquinuclidinones via a tandem amination/imination sequence: application to the synthesis of (−)-mearsine

The facile synthesis of a range of novel isoquinuclidinones from 6-acyl-cyclohex-2-enones is described, employing aqueous ammonia in a one-pot procedure involving initial conjugate addition of ammonia followed by cyclisation via intramolecular imine formation. The scope and limitations of the methodology are described as is an efficient synthesis of the Elaeocarpus alkaloid (−)-mearsine.     

Simple proof of electron beam stability in the deep-potential-wellequilibrium

It is well known that a strongly magnetized electron beam propagating in an evacuated conducting pipe can exist in either of two equilibria, one with a shallow potential well and the other with a deep potential well. A Lorentz transformation connecting the two classes of equilibria is derived. Thus, since shallow-potential-well equilibria are known to be stable, the deep-potential-well equilibria must also be. The stability of space charge waves in the two equilibria should follow the same pattern     

The influence of boundary layers on supersonic inlet flow unstart induced by mass injection

A transverse jet is injected into a supersonic model inlet flow to induce unstart. Planar laser Rayleigh scattering from condensed CO₂ particles is used to visualize flow dynamics during the unstart process, while in some cases, wall pressure traces are simultaneously recorded. Studies conducted over a range of inlet configurations reveal that the presence of turbulent wall boundary layers strongly affect the unstart dynamics. It is found that relatively thick turbulent boundary layers in asymmetric wall boundary layer conditions prompt the formation of unstart shocks; in symmetric boundary conditions lead to the propagation of pseudo-shocks; and in both cases facilitate fast inlet unstart, when compared with thin, laminar boundary layers. Incident shockwaves and associated reflections are found to affect the speed of pressure disturbances. These disturbances, which induce boundary layer separation, are found to precede the formation of unstart shocks. The results confirm the importance of and need to better understand shock-boundary layer interactions in inlet unstart dynamics.