Optimized precursor ion selection for labile ions in a linear ion trap mass spectrometer and its impact on quantification using selected reaction monitoring

The fragmentation of fragile ions during the application of an isolation waveform for precursor ion selection and the resulting loss of isolated ion intensity is well‐known in ion trap mass spectrometry (ITMS). To obtain adequate ion intensity in the selected reaction monitoring (SRM) of fragile precursor ions, a wider ion isolation width is required. However, the increased isolation width significantly diminishes the selectivity of the channels chosen for SRM, which is a serious problem for samples with complex matrices. The sensitive and selective quantification of many lipid molecules, including ceramides from real biological samples, using a linear ion trap mass spectrometer is also hindered by the same problem because of the ease of water loss from protonated ceramide ions. In this study, a method for the reliable quantification of ceramides using SRM with near unity precursor ion isolation has been developed for ITMS by utilizing alternative precursor ions generated by in‐source dissociation. The selected precursor ions allow the isolation of ions with unit mass width and the selective analysis of ceramides using SRM with negligible loss of sensitivity. The quantification of C18:0‐, C24:0‐ and C24:1‐ceramides using the present method shows excellent linearity over the concentration ranges from 6 to 100, 25 to 1000 and 25 to 1000 nM, respectively. The limits of detection of C18:0‐, C24:0‐ and C24:1‐ceramides were 0.25, 0.25 and 5 fmol, respectively. The developed method was successfully applied to quantify ceramides in fetal bovine serum. Copyright © 2014 John Wiley & Sons, Ltd.     

一种刺松藻来源的硫酸阿拉伯聚糖的制备及特征结构表征

刺松藻(Codium fragile)经水提-醇沉获得粗多糖, 进一步将刺松藻粗多糖(CFP) 通过Q-Sepharose Fast Flow(QFF) 阴离子交换柱纯化得到6个多糖组分CFP1CFP6, 其中, 在CFP6中发现纯度较高的阿拉伯聚糖. 采用高效凝胶渗透色谱与十八角激光散射仪联用法和1-苯基-3-甲基-5-吡唑啉酮(PMP)柱前衍生高效液相色谱法对CFP6的分子量及单糖组成进行了分析. 结果表明, CFP6是一种分子量为79290的多糖, 由阿拉伯糖(Ara)和半乳糖(Gal)组成, 二者摩尔比为14.8:1.0. 通过多维核磁共振波谱、 液相色谱-质谱联用及二级质谱等方法对CFP6的糖苷键连接方式及其寡糖序列结构进行表征, 进一步阐明了该复杂多糖的特征结构. 经判断, CFP6主链由Ara组成, 通过 β-(1→3)糖苷键连接, 在Ara的C2位存在分支结构, 硫酸基位于Ara的C4或C2位.     

Measuring stress intensity factors with a camera: Integrated digital image correlation (I-DIC)Mesure de facteurs d'intensité des contraintes avec une caméra : corrélation d'images numériques intégrée (CINI)

A novel ‘integrated’ approach coupling image correlation and elastic displacement field identification provides a powerful and accurate tool to evaluate mode I and II stress intensity factors. This technique is applied to silicon carbide subjected to a sandwiched three-point bend test, using digital pictures obtained in optical microscopy where the pixel physical scale is about 2 μm. A crack whose maximum opening is 500 nm can be detected and its geometry identified. The toughness is determined well within a 10%uncertainty. To cite this article: F. Hild, S. Roux, C. R. Mecanique 334 (2006).     

新型Pr基大块非晶及其特性研究

用铜模吸铸法获得了直径为5mm的一种新的Pr基大块非晶.与以往其他稀土-过渡金属(RE-TM)大块非晶不同的是，这种新的Pr基大块非晶具有明显的玻璃转变和稳定的过冷液相区，且其玻璃转变温度在目前已知的大块非晶中是最低的，T_g=409K.研究了该大块非晶的玻璃转变动力学，并给出了Kauzmann温度T_k、Vogel-Fulcher温度T⁰_g及脆性参数m等重要参数. 关键词： 大块非晶 玻璃转变 脆性参数m     

Crack tip behavior in near-surface fluid-driven fracture experiments

This Note presents experimental results for the near-tip fracture opening of fluid-driven fractures. The effect of fluid viscosity, quantified by a dimensionless parameter, was varied between tests. The tip region closely followed the classical square-root behavior from linear elastic fracture mechanics when the viscosity parameter was small. Conversely, when the viscosity parameter was of order one and the lag between the fluid-filled region and the fracture front accounted for less than 30% of the fracture, the tip region behaved according to a known intermediate asymptotic solution which results from the solid/fluid coupling. To cite this article: A.P. Bunger et al., C. R. Mecanique 333 (2005).     

New insights from variable-temperature and variable-pressure studies into coupling and decoupling processes for ion transport in polymer electrolytes and glasses

A fresh analysis of literature data shows how the influences of temperature and pressure on ion transport and structural relaxation in glass-forming systems may be combined within the framework of ‘master plots’ based on the equation E_A = M · V_A, to reveal new insights into coupling and decoupling effects in a wide range of systems. E_A,σ and V_A,σ are, respectively, instantaneous activation energies and volumes for ionic conductivity and the parameter, M_σ, is a corresponding ‘process modulus’. For structural relaxations occurring at the glass transition, the appropriate modulus is given by M_s = T_g · dP/dT_g. We can now identify typical behaviour patterns for fragile liquids on the one hand, and typical inorganic glasses on the other. Thus, the parameters, M_σ and M_s, for fragile systems such as molten Ca(NO₃)₂:KNO₃ (CKN) or a typical polymer electrolyte such as a complex of LiCF₃SO₃ in PPG, are found to remain constant over a wide range of temperatures down to T_g, despite changes in the temperature (and pressure) dependences of the ionic conductivities, as indicated for example by a return to Arrhenius behaviour in the case of CKN, or by so-called Stickel plots and changes in the VTF parameters for the polymer electrolytes. If E* and V* are activation energies and volumes assigned to elementary steps, when again E* = M · V*, we can go further and identify the microscopic processes driving forward structural relaxation. In the case of inorganic glasses, where usually we find the decoupling index R_τ ≈ 10¹², we identify two distinct decoupling paradigms represented by strong and fragile systems respectively, where in both cases the activation volumes for ion transport are very similar to the corresponding ionic volumes. In the former case (typified by the strongly cross-linked silicate and aluminosilicate systems), the negative activation volumes for structural relaxation (negative values of dT_g/dP) are clearly indicative of a ‘water-like’ behaviour attributable to the collapse of the network under pressure. On the other hand, for the more fragile fast-ion conducting silver iodomolybdate glass, the experimental results show that M_s (at T_g) ≈ M_σ (in glass), implying some recoupling of structural relaxation to ion transport. Arguments based on the dynamic structure model lead us to predict that a similar close link should exist between M_s (at T_g) and M_σ in the relatively fragile lithium and sodium borate glasses, thus highlighting the need for more information concerning the effects of pressure on the glass transition temperatures of common inorganic glasses.     

Selective Monitoring of the Enzymatic Activity of the Tumor Suppressor Fhit

Cancer is a leading cause of death worldwide. Functional inactivation of tumor suppressor proteins, mainly by mutations in the corresponding genes, is a key event in cancer development. The fragile histidine triade protein (Fhit) is a tumor suppressor that is frequently affected in different cancer types. Fhit possesses diadenosine triphosphate hydrolase activity, but although reduction of its enzymatic activity appears to be important for exerting its tumor suppressor function, the regulation of Fhit activity is poorly understood. Here, we introduce a novel fluorogenic probe that is suited to selectively analyze the enzymatic activity of Fhit in extracts derived from human cells. This novel method will allow in‐depth insight into the mechanisms involved in Fhit regulation in biologically relevant setups and, thus, into its role in the development of cancer.     

Fragile graphs with small independent cuts

A graph is called fragile if it has a vertex cut which is also an independent set. Chen and Yu proved that every graph with n vertices and at most 2n?4 edges is fragile, which was conjectured to be true by Caro. However, their proof does not give any information on the number of vertices in the independent cuts. The purpose of this paper is to investigate when a graph has a small independent cut. We show that if G is a graph on n vertices and at most (12n/7)?3 edges, then G contains an independent cut S with ∣S∣≤3. Upper bounds on the number of edges of a graph having an independent cut of size 1 or 2 are also obtained. We also show that for any positive integer k, there is a positive number ε such that there are infinitely many graphs G with n vertices and at most (2?ε)n edges, but G has no independent cut with less than k vertices. © 2002 Wiley Periodicals, Inc. J Graph Theory 41: 327–341, 2002