GC/MS分析纸浆及沉积树脂中脂肪酸组成

本文用色谱-质谱联用分析了纸浆及其沉积物的树脂中的脂肪酸成分。结果表明:纸浆中脂肪酸成分主要是油酸、9,11-十八碳二烯酸和软脂酸。沉积树脂的脂肪配成分基本上与之相同。纸浆中甘油三酸酯的脂肪酸的主要成分是油酸和软脂酸。纸浆中的甘油三酸酯是导致制浆造纸过程中产生树脂障碍的主要有害成分之一。     

Dried Blood Spots as Matrix for Evaluation of Valproate Levels and the Immediate and Delayed Metabolomic Changes Induced by Single Valproate Dose Treatment

The immediate and delayed metabolic changes in rats treated with valproate (VPA), a drug used for the treatment of epilepsy, were profiled. An established approach using dried blood spots (DBS) as sample matrices for gas chromatography/mass spectrometry-based metabolomics profiling was modified using double solvents in the extraction of analytes. With the modified method, some of the previously undetectable metabolites were recovered and subtle differences in the metabolic changes upon exposure to a single dose of VPA between males and female rats were identified. In male rats, changes in 2-hydroxybutyric acid, pipecolic acid, tetratriacontane and stearic acid were found between the control and treatment groups at various time points from 2.5 h up to 24 h. In contrast, such differences were not observed in female rats, which could be caused by the vast inter-individual variations in metabolite levels within the female group. Based on the measured DBS drug concentrations, clearance and apparent volume of distribution of VPA were estimated and the values were found to be comparable to those estimated previously from full blood drug concentrations. The current study indicated that DBS is a powerful tool to monitor drug levels and metabolic changes in response to drug treatment.     

固相微萃取和GC/MS分析JOB炸药老化释放气氛

采用3种不同吸附性能萃取头的固相微萃取器对JOB炸药在自然密封存放和加热老化一定时间后所释放出来的微量气氛进行了萃取吸附研究，采用GC／MS测试技术对其进行了定性分析。研究结果表明，固相微萃取装置对该炸药老化过程中释放的微量无机气体和有机挥发性组分具有选择性吸附和萃取浓缩作用，峰强度显示不同老化条件下放出的气体组分和含量具有不同的结果。初步探讨了老化释放气体的机理，JOB炸药老化放出的主要是一些合成溶剂、杂质等。     

LC-MS/MS法测定人全血中环孢素A浓度及环孢素眼用乳剂健康人体药代动力学研究

建立液相色谱 质谱联用法测定人全血中环孢素A浓度,选用Kromasil-C₁₈色谱柱（20 mm×4.6 mm×5 μm）,以甲醇1 mmol•L^-1甲酸铵溶液为流动相,采用梯度洗脱进行分离,样品用沉淀蛋白法处理后进样,流速1.1 mL•min^-1,柱温60 ℃,进样量20 μL。选用3200 QTrap型三重四极杆串联质谱仪的多重反应监测（MRM）扫描方式进行检测。环孢素A的线性范围为0.2~20.00 μg•L^-1,定量下限为0.2 μg•L^-1。准确度与精密度结果显示,方法日间、日内变异均小于15%,相对偏差为-12.60%~12.80%,方法提取回收率为（98.1±4.7）%,稳定性较好。所建立的方法快速、灵敏、专属性强、重现性好,可用于环孢素眼用乳剂健康人体药代动力学研究。     

Simulation of retronasal aroma of white and red wine in a model mouth system. Investigating the influence of saliva on volatile compound concentrations

The influence of saliva on aroma release from white and red wines was studied in a model mouth system. Aroma compounds were analysed in the dynamic headspace of wines by solid phase micro extraction/gas chromatography with flame ionization detection. Volatile compounds were identified by solid phase micro extraction/gas chromatography-mass spectrometry, resulting in a total of 43 compounds in white wine and 41 in red wine. The results showed a greater influence of saliva on aroma release in white wine than red wine. In white wine treated with human saliva, esters and fusel alcohols, responsible for fruity and fusel oil odours, were reduced of 32–80%; by contrast, the concentration of 2-phenylethanol and furfural, responsible for rose and toasted almond notes, increased by 27% and by 155%, respectively. In red wine, treated with human saliva, only a few esters decrease, with a reduction of 22–51% due to protein-binding ability of polyphenols that are able to inhibit the activity of the saliva. C-13 norisoprenoids, vitispirane (eucalyptol) and TDN (kerosene), decreased both in white and red wine, showing a comparable variation while, for β-damascenone, the variation was insignificant.     

复合衰落信道下分布式MIMO系统中断概率及信道容量分析

针对分布式MIMO系统中断概率和信道容量这2大性能指标,在复合衰落信道模型下,当上行链路采用最大比发送—选择合并,下行链路采用选择发送—最大比合并时,利用Lognormal分布对复杂Gamma-Lognormal分布的近似,推导得到当移动台位置给定时,系统中断概率和信道容量的闭合表达式,证明了系统性能指标与移动台分布之间存在密切的联系;随后依照实际通信环境,提出一种考虑存在小区热点的移动台非均匀分布模型,然后推导得到考虑该分布模型后的系统平均中断概率和平均信道容量闭合表达式;最后通过计算机仿真,证明了所提近似处理的精确性以及各项理论分析的合理性。     

Critical Ratios for structural analysis of triacylglycerols using mass spectrometry

Recent developments have finally allowed fragment behaviors using APCI‐MS to be elucidated after twenty years of literature reports. Critical Ratios have been defined that correspond to various aspects of triacylglycerol (TAG) analysis, from overall degree of unsaturation to localization of fatty acids on the glycerol backbone (regioisomers), to grouping of unsaturated fatty acids. The same ratios also constitute a compact library of TAG mass spectra.     

Mining the Wheat Grain Proteome

Bread wheat is the most widely cultivated crop worldwide, used in the production of food products and a feed source for animals. Selection tools that can be applied early in the breeding cycle are needed to accelerate genetic gain for increased wheat production while maintaining or improving grain quality if demand from human population growth is to be fulfilled. Proteomics screening assays of wheat flour can assist breeders to select the best performing breeding lines and discard the worst lines. In this study, we optimised a robust LC–MS shotgun quantitative proteomics method to screen thousands of wheat genotypes. Using 6 cultivars and 4 replicates, we tested 3 resuspension ratios (50, 25, and 17 µL/mg), 2 extraction buffers (with urea or guanidine-hydrochloride), 3 sets of proteases (chymotrypsin, Glu-C, and trypsin/Lys-C), and multiple LC settings. Protein identifications by LC–MS/MS were used to select the best parameters. A total 8738 wheat proteins were identified. The best method was validated on an independent set of 96 cultivars and peptides quantities were normalised using sample weights, an internal standard, and quality controls. Data mining tools found particularly useful to explore the flour proteome are presented (UniProt Retrieve/ID mapping tool, KEGG, AgriGO, REVIGO, and Pathway Tools).     

应用高效液相色谱-电感耦合等离子体质谱联用技术分析研究畜肉中硒形态

目的 应用高效液相色谱-电感耦合等离子体质谱联用技术（HPLC-ICP/MS）分析研究畜肉中Se（Ⅵ）、Se（Ⅳ）、SeCys、MeSeCys和SeMet 5种硒形态。方法 采用超声辅助蛋白酶ⅩⅣ和胰脂肪酶酶解提取畜肉中硒形态,以C18反相色谱柱为分析柱,10 mmol/L柠檬酸和5 mmol/L己烷磺酸钠（pH=4.0,含1%甲醇）为流动相,等度洗脱,HPLC-ICP/MS分析。结果 5种硒形态可在7 min内有效分离,在线性范围内相关系数均>0.999,线性良好;Se（Ⅵ）、SeCys、MeSeCys和SeMet 4种硒形态检出限为0.000 3~0.002 mg/kg,不同浓度水平的加标回收率为80.0%~103.3%,相对标准偏差均小于6.8%,有证标准物质ERM^? BC210a测定值在标准值范围内。结论 该方法适用畜肉中Se（Ⅵ）、SeCys、MeSeCys和SeMet的分析测定。畜肉中的硒形态主要为SeMet,同时含有少量的MeSeCys和SeCys。     

Functional Characterization of the Solute Carrier LAT-1 (SLC7A5/SLC2A3) in Human Brain Capillary Endothelial Cells with Rapid UPLC-MS/MS Quantification of Intracellular Isotopically Labelled L-Leucine

The solute carrier L-type amino acid transporter 1 (LAT-1/SLC7A5) is a viable target for drug delivery to the central nervous system (CNS) and tumors due to its high abundance at the blood–brain barrier and in tumor tissue. LAT-1 is only localized on the cell surface as a heterodimer with CD98, which is not required for transporter function. To support future CNS drug-delivery development based on LAT-1 targeting, we established an ultra-performance liquid chromatography–tandem mass spectrometry (UPLC-MS/MS) assay for stable isotopically labeled leucine ([¹³C₆, ¹⁵N]-L-leucine), with a dynamic range of 0.1–1000 ng/mL that can be applied for the functional testing of LAT-1 activity when combined with specific inhibitors and, consequently, the LAT-1 inhibition capacity of new compounds. The assay was established in a 96-well format, facilitating high-throughput experiments, and, hence, can support the screening for novel inhibitors. Applicable recommendations of the US Food and Drug Administration and European Medicines Agency for bioanalytical method validation were followed to validate the assay. The assay was applied to investigate the IC₅₀ of two well-known LAT-1 inhibitors on hCMEC/D3 cells: the highly specific LAT-1 inhibitor JPH203, which was also used to demonstrate LAT-1 specific uptake, and the general system L inhibitor BCH. In addition, the [¹³C₆, ¹⁵N]-L-leucine uptake was determined on two human brain capillary endothelial cell lines (NKIM-6 and hCMEC/D3), which were characterized for their expressional differences of LAT-1 at the protein and mRNA level and the surface amount of CD98. The IC₅₀ values of the inhibitors were in concordance with previously reported values. Furthermore, the [¹³C₆, ¹⁵N]-L-leucine uptake was significantly higher in hCMEC/D3 cells compared to NKIM-6 cells, which correlated with higher expression of LAT-1 and a higher surface amount of CD98. Therefore, the UPLC-MS/MS quantification of ([¹³C₆, ¹⁵N]-L-leucine is a feasible strategy for the functional characterization of LAT-1 activity in cells or tissue.