毛细管电泳质谱联用技术及其应用

本文介绍了用于毛细管电泳质谱联用仪器的多种接口技术，描述了ＣＺＥ，ＣＩＥＦ，ＣＧＥ，ＭＥＫＣ和ＣＩＴＰ等毛细管电泳技术和四极质谱，离子阱质谱，傅 叶变换离子回旋共振质谱，飞行时间质谱，磁质谱，解吸质谱等联用的现状及发展前景，对近年来ＣＥ－ＭＳ在酶解产物。蛋白质和肽，核苷酸，药物及代谢产物等领域中的应用作了详细述评。     

毛细管电泳及其质谱联用技术分析重组人促红细胞生成素

用高效毛细管电泳测定了重组人促红细胞生成素（ｒｈＥＰＯ）的微多相性、肽图，同时采用毛细管电泳质谱联用技术鉴定了部分非糖基化胰酶消解片段和Ｏ－１２６糖基化肽的结构。方法简便、快速，适用于ｒｈＥＰＯ半成品的质量控制。     

毛细管电泳-电喷雾质谱联用技术及其在蛋白质分析领域中的应用

综述了毛细管电泳与电喷雾质谱联用的接口技术、分离模式及其在蛋白质分析领域中的应用，特别是毛细管等电聚焦与电喷雾质谱联用在蛋白质组学中研究进展。     

A New Immunoassay Method by Capillary Electrophoresis with Enhanced Chemiluminescence Detection

Immunoassay based on capillary electrophoresis has recently been paid a great attention due to its excellent separation power, high analysis speed, small sample volume requirements, and automation 1,2. Since the injection volume is too small, immunoassay by CE needs an extremely sensitive detector. Laser-induced fluorescence3 and electro-chemical detections 4 have been used for this purpose. In fact chemilumi- nescence (CL) is also a highly sensitive method for detection, and is widely used …     

Capillary Electrophoresis/Electrospray Mass Spectrometry of Seven Triazine Pesticides

The on-line micellar electrokinetic chromatography and electrospray ionization mass spectrometry (MEKC-ESI/MS) was used for the determination of seven triazine pesticides.     

蛋白质组学质谱平台肽段可检测性预测研究进展

生物质谱是蛋白质组研究中的核心技术之一,可以实现大规模、高通量的蛋白质定性和定量分析。由于样品和实验过程自身的复杂性,质谱实验的重复性还存在一些问题,肽段鉴定和定量结果有很大的随机性,肽段的质谱检测概率问题在蛋白质组研究中,特别是定量蛋白质组研究中备受关注。本文总结了影响肽段可检测性的重要因素,分析了已经提出的计算预测方法,并对其在实验研究中的应用进行了综述。     

Fractionation of Dissolved Organic Matter on Coupled Reversed-Phase Monolithic Columns and Characterisation Using Reversed-Phase Liquid Chromatography-High Resolution Mass Spectrometry

Eleven Onyx monolithic C₁₈ columns (100 x 3 mm) were connected in series to obtain a high-capacity reversed-phase HPLC column providing 110,000 theoretical plates. The column was used to fractionate a complex mixture of semi-polar and apolar components within marine dissolved organic matter (DOM), isolated using solid-phase extraction (SPE) on poly(styrene–divinylbenzene) cartridges, and Suwannee River natural organic matter, isolated by reverse osmosis. In each case, 15 isolated fractions were further separated using a second-dimension reversed-phase HPLC coupled with high-resolution mass spectrometry. Successful fractionation of the major compositional materials within DOM (i.e. carboxylic-rich alicyclic molecules, CRAM) in order of decreasing polarity was confirmed. Upon formulae assignment, homologous series of compounds were fractionated according to decreasing O/C ratio and increasing H/C ratio. Different compounds with the same exact masses were separated across six fractions, highlighting the immensely complex nature of the material, with the presence of potentially hundreds of molecules for each molecular formula. Both samples showed clear compositional differences not only related to source (seawater or freshwater), but also to the extraction method applied (SPE or reverse osmosis).     

多肽电泳结合质谱技术在血清多肽组学研究中的应用

近年来,多肽组作为蛋白组的补充部分,被众多研究者所瞩目,血清多肽标志物用于临床诊断的报道越来越多[1].     

Determination of Catecholamines by Capillary Electrophoresis and Reversed-Phase High-Performance Liquid Chromatography

A method is proposed for the electrophoretic determination of adrenaline, noradrenaline, and dopamine with mass-spectrometric or UV detection. A procedure is proposed for the sample preparation of biological fluids with the use of solid-phase extraction on alumina. A comparative assessment of the determination of catecholamines by capillary electrophoresis and reversed-phase high-performance liquid chromatography was performed.     

Comparative Study of Three Methods for Affinity Measurements: Capillary Electrophoresis Coupled with UV Detection and Mass Spectrometry, and Direct Infusion Mass Spectrometry

We present affinity capillary electrophoresis and mass spectrometry (ACE-MS) as a comprehensive separation technique for label-free solution-based affinity analysis. The application of ACE-MS for measuring affinity constants between eight small molecule drugs [ibuprofen, s-flurbiprofen, diclofenac, phenylbutazone, naproxen, folic acid, resveratrol, and 4,4'-(propane-1,3-diyl) dibenzoic acid] and β-cyclodextrin is described. We couple on-line ACE with MS to combine the separation and kinetic capability of ACE together with the molecular weight and structural elucidation of MS in one system. To understand the full potential of ACE-MS, we compare it with two other methods: Direct infusion mass spectrometry (DIMS) and ACE with UV detection (ACE-UV). After the evaluation, DIMS provides less reliable equilibrium dissociation constants than separation-based ACE-UV and ACE-MS, and cannot be used solely for the study of noncovalent interactions. ACE-MS determines apparent dissociation constants for all reacting small molecules in a mixture, even in cases when drugs overlap with each other during separation. The ability of ACE-MS to interact, separate, and rapidly scan through m/z can facilitate the simultaneous affinity analysis of multiple interacting pairs, potentially leading to the high-throughput screening of drug candidates.     

pH对毛细管电泳分离多肽的影响

设计了一个针对高年级本科生的毛细管电泳分离实验，用以研究pH对生物小分子多肽分离的影响。5种多肽包括Bradykinin、[Hyp3]-bradykinin、Angiotensin I、Leucine Enkephalin和[Met5]-Enkaphalin，被用于毛细管电泳的分离实验。研究了毛细管电泳生物分析实验中最重要的2个因素即电渗流和样品吸附随pH的变化以及对于分离的影响。在pH=10的条件下，酸性多肽几乎没有吸附，少量的碱性多肽有吸附。在pH=6的条件下，碱性多肽具有非常强的吸附从而导致非常差的分离效果，在pH=2.3的条件下，5种多肽都能被很好地分离，由于多肽此时都带有正电荷因此几乎没有吸附。而在此pH，电渗流消失。对具有一定分析化学基础理论知识的学生而言，这是一个非常好的生物分析实验，有助于学生充分理解相关环境因素对仪器分析的重要影响。     

毛细管电泳-电感耦合等离子质谱联用的接口设计

描述了毛细管电泳电感耦合等离子体质谱(CE-ICP-MS)联用技术的单T型接口,自行设计了双T型接口,并对两接口的分析性能作了比较。解决了接口中的常见问题,使用节流阀减小自吸作用并降低了CE分离物的稀释倍数,排气阀使提升量保持稳定。经考察得知,采用自吸作用提升液流流量稳定,其重现性RSD小于5％;双T型接口较单T型接口对CE分离更有利。采用双T型接口联用时,CE分离La、Ce、Nd混合离子迁移时间RSD小于2％,MS信号RSD小于15％,且不同浓度样品经CE分离后其MS信号基本呈线性关系。     

毛细管电泳安培型电化学检测法

本文评述了近年来安培型电化学检测法在毛细管电泳中的发展概况，归纳了二种检测方式及其装置的结构特点。阐述了金属电极、液膜电极和修饰电极等在电化学检测应用研究中的作用以及此方法在微区分析、活体分析中的重要意义，并展望了其发展前景。     

毛细管电泳电化学检测

综述了毛细管电泳的电化学检测,包括电位法、电导法和安培法检测的研究进展,重点讨论了电化学检测与毛细管电泳的耦联,并对电化学检测的原理及其应用进行了较详细的叙述,引用文献72篇。     

毛细管电泳化学发光在线检测

评论了毛细管区带电泳化学发光检测联用技术这一新兴的研究领域。化学发光检测具有背景低、热力学范围宽、灵敏度高的优点，适于毛细管电泳柱后微量样品的在线检测。论述了该检测器与毛细管电泳联用的接口和应用状况。     

基于PMMA毛细管电泳芯片的多位点突变检测研究

利用基于激光诱导荧光(LIF)检测的芯片毛细管电泳平台,批量制作了低成本聚甲基丙烯酸甲酯(PMMA)芯片,通过修饰管道,优化有效分离距离、分离介质等条件,可在90s内完成DNA片段的分离检测,实现单碱基分离,并在此平台上成功地对遗传性耳聋三个常见突变位点实现分型检测,为这种低成本的PMMA芯片应用于分型相关的临床诊断领域奠定了基础。     

Conformational Dynamics of DNA G-Quadruplex in Solution Studied by Kinetic Capillary Electrophoresis Coupled On-line with Mass Spectrometry

Invited for this months cover is the group of Prof. Maxim V. Berezovski. The cover picture shows the two-dimensional separation of unfolded (green) and folded (red) forms of G-quadruplex (GQ) DNA. The first dimension is kinetic capillary electrophoresis (KCE) separation of unfolded and folded DNA with different K⁺ concentrations in solution; the second dimension is ion mobility mass spectrometry separation of DNA conformers in the gas phase. DNA folding into a compact GQ structure is mediated by K⁺ ions. For more details, see the Full Paper on p. 58 ff.     

High-Throughput Screening of Ten Microcystins and Nodularins, Cyanobacterial Peptide Hepatotoxins, by Reversed-Phase Liquid Chromatography-Electrospray Ionisation Mass Spectrometry

Liquid chromatography-electrospray ionisation mass spectrometry was evaluated in the high-throughput analysis of microcystins and nodularins, cyanobacterial peptide hepatotoxins. Extracts originating from cyanobacterial strains and field material were separated on a 30 mm × 4 mm I.D. Merck Purospher STAR RP-18e column using a rapid gradient of aqueous formic acid and acetonitrile, ionised by electrospray technique and analysed on a Micromass Quattro II triple-quadrupole mass spectrometer operated in the selected ion recording (SIR) mode. The total analysis time per sample was 2.8 min corresponding to 514 samples a day. The system showed good robustness during a series of 320 repetitive injections of a field sample containing three major microcystins.     

毛细管电泳及芯片毛细管电泳的电容耦合非接触电导检测

综述了毛细管电泳(CE)及芯片毛细管电泳(MCE)的电容耦合非接触电导检测(Capacitively Coupled Contactless Conductivity detection,C4D)的研究状况;并分别对其装置、检测的影响因素及其应用进行了评述。引用文献81篇。     

质谱分析福尔马林固定组织的多肽谱

福尔马林固定组织时,甲醛与蛋白质多肽链的氨基酸侧链上的功能基团,特别是氨基、亚氨基、酰氨基、羟基和巯基等相结合,使蛋白分子间形成大分子网络,蛋白不再发生迁移达到固定目的[1].