GC/MS和ESI/MS/MS同位素内标法检测甲基丙二酸血症

以甲基丙二酸血症为对象,分别用GC/MS和ESI/MS/MS方法对该疾病进行了定性和定量检测.通过对样品前处理和分离条件的改善,对疾病的标识化合物之一甲基丙二酸进行了定量测定,其稳定性、精密度和回收率结果很好.同时比较了GC/MS和ESI/MS/MS两种方法的特点,发现两种方法的结合不仅可满足新生儿代谢疾病筛查的要求,同时还可对高危人群进行诊断.     

稳定同位素iTRAQ标记/高效液相色谱-串联质谱法同时定量分析人体中42种氨基酸及典型病例

建立稳定同位素iTRAQ标记/高效液相色谱-串联质谱法同时定量分析人体中42种氨基酸的方法.人生物样本经磺基水杨酸沉淀蛋白,稳定同位素iTRAQ-115衍生化后,加入iTRAQ-114同位素标记的氨基酸内标液进样,选用AAA-C18色谱柱,以水乙腈(含有0.01％七氟丁酸、0.1％甲酸)为流动相,采用梯度洗脱进行分离,选用3200QTRAP型质谱仪的多重反应监测(MRM)扫描方式进行检测.同位素内标消除了系统误差,实现了氨基酸的定量分析,42种氨基酸及同分异构体均能基线分离.本方法快速、灵敏、专属性强、高通量,可用于临床氨基酸代谢疾病的诊疗和营养评估.     

Automated Precursor Ion Exclusion During LC-MS/MS Data Acquisition for Optimal Ion Identification

Liquid chromatography-tandem mass spectrometry (LC-MS/MS) is widely used for characterizing multiple samples of complex mixtures with similar compositions. This article addresses a data acquisition strategy for collecting a maximal number of unique, high-quality MS/MS during LC-MS/MS analysis of multiple samples. Based on the concept that a component only needs to be identified once when analyzing multiple samples with similar compositions, an automated intersample data-dependent acquisition strategy was developed. The strategy is based on precursor ion exclusion (PIE) and is implemented in MassAnalyzer in an automated fashion for Thermo Scientific (San Jose, CA, USA) mass spectrometers. In this method, MassAnalyzer submits one sample at a time to the sample queue. After data acquisition of each sample, MassAnalyzer automatically analyzes the data to generate a PIE list based on the MS/MS precursor ions, merges this list with the list generated from previous runs, adds the list to the MS method file, and submits the next sample to the queue. The PIE list contains both m/z value and time window for each precursor ion, and is generated intelligently so that if an MS/MS is insufficient for identifying the peak of interest, it will be collected again near the top of the peak in the next run. Therefore, the strategy maximizes both quality and the number of unique MS/MS. When automated PIE was used to acquire LC-MS/MS data of an antibody tryptic digest and a soy hydrolysate sample, the number of identified ions increased by 52% and 93%, respectively, compared with data acquired without using PIE.     

Application of Derivatization Gas Chromatography/Mass Spectrometry for the Identification and Quantitation of Pinitol in Plant Roots

Abstract

Pinitol (D-3-O-methyl-chiro-inositol), a cyclitol, has a variety of roles in plant biology, and is being used as a nutritional supplement. These applications increase the importance of finding new methods for determining the pinitol content in plant tissues. A reliable method for the identification and quantitation of pinitol using trimethylsilyl imidazole (TMSI) derivatization and gas chromatography/mass spectrometry (GC/MS) was developed. One major ion fragment, m/z 260, was used to quantify pinitol in three plant species. Soybeans contained approximately 1.9 mg/g wet weight pinitol while levels in sugar beets and snap beans were below detection limits.     

一种用于检测PO43-离子、Fe3+离子和硝基芳香爆炸物的水稳定发光Zn-配合物传感器

基于3-（2,4-二羧基苯基）-6-羧基吡啶配体（H₃dpcp）,利用溶剂热法制备了发光配合物[Zn（H₂dpcp）₂（H₂O）₂]·H₂O（1）。配合物1具有新颖的单核蝴蝶状结构,通过π…π相互作用延伸成三维超分子结构。实验结果表明,配合物1在pH=1~10的水溶液中表现出优异的发光稳定性。值得注意的是,配合物1不仅可以利用荧光增强效应高选择性和可循环性地检测PO₄^3-离子,并且Fe³⁺离子可以使配合物1的发光显著猝灭。对硝基芳香族爆炸物的荧光传感实验表明,配合物1可以作为发光探针高选择性、灵敏性地检测2,4,6-三硝基苯酚（TNP）,同时具有较低的检测限。此外,还详细探究了配合物1对上述分析物的发光传感机理。     

Improved Stability of a Stable Crystal Form C of 6S-5-Methyltetrahydrofolate Calcium Salt,Method Development and Validation of an LC–MS/MS Method for Rat Pharmacokinetic Comparison

Folate is a vitamin beneficial for humans that plays an important role in metabolism, but it cannot be well supplemented by food; it is necessary to supplement it in other ways. Based on this consideration, a novel crystal form C of 6S-5-methyltetrahydrofolate calcium salt (MTHF CAC) was obtained. To explore the difference between MTHF CAC and the crystal form Ⅰ of 6S-5-methyltetrahydrofolate calcium salt (MTHF CA) as well as an amorphous product of 6S-5-methyltetrahydrofolate glucosamine salt (MTHF GA), their stability and pharmacokinetic behaviours were compared. The results of high-performance liquid chromatography coupled with ultraviolet detection analysis indicated that MTHF CAC showed a better stability than MTHF CA and MTHF GA. After oral administration of MTHF CAC, MTHF CA, and MTHF GA to male rats, the MTHF concentrations were analysed using a validated liquid chromatography–tandem mass spectrometry, and the pharmacokinetic parameters were compared. The mean residence times (0–t) of MTHF CAC, MTHF CA, and MTHF GA were 3.7 ± 1.9 h, 1.0 ± 0.2 h (p < 0.01), and 1.5 ± 0.3 h (p < 0.05), respectively. The relative bioavailability of MTHF CAC was calculated to be 351% and 218% compared with MTHF CA and MTHF GA, respectively, which suggests that MTHF CAC can be better absorbed and utilized for a longer period of time.     

Integrating Enhanced Profiling and Chemometrics to Unveil the Potential Markers for Differentiating among the Leaves of Panax ginseng,P. quinquefolius,and P. notoginseng by Ultra-High Performance Liquid Chromatography/Ion Mobility-Quadrupole Time-of-Flight Mass Spectrometry

The leaves of Panax species (e.g., Panax ginseng-PGL, P. quinquefolius-PQL, and P. notoginseng-PNL) can serve as a source for healthcare products. Comprehensive characterization and unveiling of the metabolomic difference among PGL, PQL, and PNL are critical to ensure their correct use. For this purpose, enhanced profiling and chemometrics were integrated to probe into the ginsenoside markers for PGL/PQL/PNL by ultra-high performance liquid chromatography/ion mobility-quadrupole time-of-flight mass spectrometry (UHPLC/IM-QTOF-MS). A hybrid scan approach (HDMS^E-HDDDA) was established achieving the dimension-enhanced metabolic profiling, with 342 saponins identified or tentatively characterized from PGL/PQL/PNL. Multivariate statistical analysis (33 batches of leaf samples) could unveil 42 marker saponins, and the characteristic ginsenosides diagnostic for differentiating among PGL/PQL/PNL were primarily established. Compared with the single DDA or DIA, the HDMS^E-HDDDA hybrid scan approach could balance between the metabolome coverage and spectral reliability, leading to high-definition MS spectra and the additional collision-cross section (CCS) useful to differentiate isomers.