凝胶渗透色谱结合气相色谱-负化学源质谱法分析鱼肉及鱼油中的多溴联苯醚和得克隆阻燃剂

建立了凝胶渗透色谱(GPC)结合气相色谱-负化学源质谱(GC-NCI/MS)检测鱼肉及鱼油中8种多溴联苯醚(PBDEs)同系物及2种得克隆阻燃剂(DP)的分析方法。试样中加入内标物BDE-77和13C12-BDE-209后进行索氏提取,提取液经自动GPC系统除脂,多层硅胶层析柱净化后,在15 m长的毛细管气相色谱柱上分离,NCI/MS以选择离子监测方式检测目标化合物。以鱼肉样品为基质,当PBDEs的加标水平为0.2 ng/g和2 ng/g、BDE-209和DP的加标水平相应提高10倍时,其平均加标回收率为71.1%～121.4%,相对标准偏差为2.96%～13.31%(n=5);以信噪比(S/N)为3计算方法的检出限(LOD)为2.2～39.8 ng/kg。用该方法检测市售鱼肉及鱼油样品,其中多溴联苯醚总含量为2.18～15.93 ng/g,以BDE-209、BDE-47为主,两种DP均未检出。该方法准确、灵敏度高,能够满足富含脂质的动物性样品中痕量DP和PBDEs残留的分析要求。     

Analysis of questioned documents: A review

During the last years (2000–2014), many publications concerning the forensic analysis of questioned documents have been published, and new techniques and methodologies are nowadays employed to overcome forensic caseworks. This article reviews a comprehensive collection of the works focused on this issue, including dating studies, the analysis of inks from pens and printers, the analysis of paper, the analysis of other samples related to questioned documents and studies on intersecting lines. These sections highlight the most relevant analytical studies by a wide range of analytical techniques. Separation and spectrometric techniques are critically discussed and compared, emphasizing the advantages and disadvantages of each one. Finally, concluding remarks on the research published are included.     

Detection and quantification of plasma amyloid-β by selected reaction monitoring mass spectrometry

Amyloid-β (Aβ) in human plasma was detected and quantified by an antibody-free method, selected reaction monitoring mass spectrometry (SRM-MS) in the current study. Due to its low abundance, SRM-based quantification in 10 μL plasma was a challenge. Prior to SRM analysis, human plasma proteins as a whole were digested by trypsin and high pH reversed-phase liquid chromatography (RPLC) was used to fractionate the tryptic digests and to collect peptides, Aβ_1–5, Aβ_6–16, Aβ_17–28 and Aβ_29–40(42) of either Aβ_1–40 or Aβ_1–42. Among those peptides, Aβ_17–28 was selected as a surrogate to measure the total Aβ level. Human plasma samples obtained from triplicate sample preparations were analyzed, obtaining 4.20 ng mL⁻¹ with a CV of 25.3%. Triplicate measurements for each sample preparation showed CV of <5%. Limit of quantification was obtained as 132 pM, which corresponded to 570 pg mL⁻¹ of Aβ_1–40. Until now, most quantitative measurements of Aβ in plasma or cerebrospinal fluid have required antibody-based immunoassays. Since quantification of Aβ by immunoassays is highly dependent on the extent of epitope exposure due to aggregation or plasma protein binding, it is difficult to accurately measure the actual concentration of Aβ in plasma. Our diagnostic method based on SRM using a surrogate peptide of Aβ is promising in that actual amounts of total Aβ can be measured regardless of the conformational status of the biomarker.     

Properties of low temperature swelling hydrogels prepared with partially saponified PVA and drug release using the hydrogels

The hydrogels prepared by the crosslinking of partially saponified poly(vinyl alcohol) (PVA) which has low critical solution temperature (LCST) in water showed characteristics of swelling at low temperature and shrinkage at high temperature. The hydrogels showed repeatable swelling–shrinking behavior. The hydrogels containing release substances such as cyanocobalamin, p‐acetamidophenol, insulin and ovalbumin were prepared by dipping these aqueous solutions and the release substances were studied. Insulin and ovalbumin were not absorbed by the hydrogels when the use of partially PVA with the degrees of polymerization (DPs) of 540 were prepared, but absorbed by the hydrogels with DPs of 1860. The size of the polymer network prepared with a higher DP was suitable for the absorption of insulin and ovalbumin. In accordance with release substances, the release patterns were different. In this way, the polymer network sizes and their swelling behaviors of partially saponified PVAs were estimated. Copyright © 2003 John Wiley & Sons, Ltd.     

Mercerization and acid hydrolysis of bacterial cellulose

Structural changes in never- dried, disintegrated bacteria l cellulose by treatment with aqueous NaOH were examined by electron microscopy, X-ray diffractometry and acid hydrolysis behaviour and compared with those of cotton cellulose. The microfibril kept its fibrillar morphology after treatment with NaOH solutions of less than 9% (w/w), but changed into irregular aggregates when treated with NaOH above 12% (w/w), corresponding to the crystal conversion to cellulose II. The crystallinity of the resulting cellulose II was very low after a brief alkali treatment, but was increased significantly by elongated treatment (up to 10 days). In contrast, cotton cellulose was converted to cellulose II of fairly high crystallinity by alkali treatment of as little as 3 min duration, and the crystallinity did not change with longer treatments. The leveling-off degree of polymerization (LODP) of bacterial cellulose was decreased from 150 to 50 by 18% (w/w) NaOH treatment, while that of cotton linter decreased from 260 to 70. These characteristic differences between cotton linter cellulose and bacterial cellulose can be ascribed to a basic difference in microfibrillar organization in these materials: the microfibrils in cotton cellulose are in close contact with neighbouring microfibrils having opposite polarity, and in bacterial cellulose are isolated from each other and require chain folding to form the antiparallel cellulose II crystal     

嵌入式Linux设备的高精度IEEE 1588时钟同步实现

IEEE 1588时钟同步协议用于解决分布式网络测控系统中远距离仪器设备之间的同步问题;在分析IEEE 1588时钟同步实现原理的基础上,提出一种嵌入式Linux设备的高精度IEEE 1588时钟同步实现方案;采用专用PHY芯片DP83640在物理层为PTP报文加盖硬件时间戳,设计网络设备驱动与PTP硬件时钟控制驱动,并在用户层利用Linux系统标准API实现IEEE 1588协议软件;实验结果表明,两台设备直接相连时,时钟同步精度可稳定在±100 ns以内。     

Finite element and experimental method for analyzing the effects of martensite morphologies on the formability of DP steels

Abstract

In this article, we investigated the effect of martensite morphology on the mechanical properties and formability of dual phase steels. At first, three heat treatment cycles were subjected to a low-carbon steel to produce ferrite–martensite microstructure with martensite morphology of blocky-shaped, continuous, and fibrous. Tensile tests were then carried out so as to study mechanical properties, particularly the strength and strain hardening behavior of dual phase steels. In order to study the formability of dual phase samples, Forming Limit Diagram was obtained experimentally and numerically. Experimental forming limit diagram was obtained using Nakazima forming test, while Finite Element Method was utilized to numerically predict the forming limit diagram. The results indicated that the dual phase samples with fibrous martensite morphology had the highest tensile properties and strain rate hardening out of the three different microstructures. Blocky-shaped martensite morphology, on the other hand, had the worst mechanical properties. The study of the strain hardening behavior of dual phase sample by Kocks–Mecking-type plots, evinced two stages of strain hardening for all specimens with different microstructures: stages III and IV. The forming limit diagram of dual phase steels also proved that samples with fibrous martensite morphology had the best formability compared to other two microstructures. The simulated forming limit diagram manifested that there is a good agreement between experimental results and those obtained by FEM.     

Elastic-plastic behaviour of dual-phase, high-strength steel under strain-path changes

The elastic-plastic behaviour of dual-phase, high-strength steel sheets under two-stage strain-path changes has been investigated. Three different loading sequences, namely monotonic, 45° tensile path changes and orthogonal tensile path changes complied by sequences of simple uniaxial tensile tests, were analysed at room temperature. From the experiments, it was found that there is a considerable reduction of the initial flow stress over the strain-path changes. The transient softening phenomenon is observed to be a function of orientation, and the period of the transient behaviour following the strain-path change is lengthened with the amount of pre-strain. A constitutive model is adopted that includes combined isotropic and kinematic hardening and is capable of describing the marked transient softening behaviour after the pre-straining. The experimental stress–strain behaviour subsequent to the strain path change is predicted with reasonable accuracy, while the model fails to accurately describe the transient, deformation-induced anisotropy in the plastic flow.     

Two‐dimensional correlation gel permeation chromatography study of aggregate–aggregate interactions during acid‐catalyzed polymerization of triethoxysilyl‐terminated polystyrene

The three‐step polymerization of a well‐defined polymeric silane coupling agent, triethoxysilyl‐terminated polystyrene, catalyzed by acid (H₃PO₄), was traced as a function of the reaction time with gel permeation chromatography (GPC). Time‐resolved GPC traces collected during the polymerization process were then used to construct two‐dimensional (2D) correlation maps via generalized 2D correlation analysis. The results demonstrated that the synchronous and asynchronous 2D correlation GPC spectra directly reflected the dynamic variation of aggregate–aggregate interactions during each step of the polymerization. In particular, it was found that the formation of aggregates among the cyclic trimers (or tetramers) and monomers was critical for the preferential production of pentamers in the reaction system. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3447–3460, 2004