MASS SPECTROMETRY ANALYSIS OF DRUGS OF ABUSE: CHALLENGES AND EMERGING STRATEGIES

Mass spectrometry has been the “gold standard” for drugs of abuse (DoA) analysis for many decades because of the selectivity and sensitivity it affords. Recent progress in all aspects of mass spectrometry has seen significant developments in the field of DoA analysis. Mass spectrometry is particularly well suited to address the rapidly proliferating number of very high potency, novel psychoactive substances that are causing an alarming number of fatalities worldwide. This review surveys advancements in the areas of sample preparation, gas and liquid chromatography-mass spectrometry, as well as the rapidly emerging field of ambient ionization mass spectrometry. We have predominantly targeted literature progress over the past ten years and present our outlook for the future. © 2020 Periodicals, Inc. Mass Spec Rev     

液相色谱-串联质谱法定量分析人血浆中曲克芦丁

A sensitive and specific liquid chromatography-tandem mass spectrometry method was developed and validated to quantify troxerutin in human plasma using rutin as the internal standard. After a simple protein precipitation with perchloric acid, the post-treatment samples were analyzed on a Phenomenex Synergi Fusion RP column interfaced with a tripe-quadrupole tandem mass spectrometer using positive electrospray ionization. The assay was linear over the concentration range 31.25-4 000 pg/mL using a 20 μL aliquot of plasma. The correlation coefficients for the calibration curves ranged from 0.999 5 to 0.999 6. The intra-and inter-day precisions over the entire concentration were not more than 13.5%. Acetonitrile and water (20∶80, v/v) is used as the isocratic mobile phase, with 0.1% of formic acid in water. The method was successfully applied for pharmacokinetic study after a single oral administration of 300 mg troxerutin to 18 healthy volunteers.     

中药多成分药代动力学分析技术研究进展

中药多成分药代动力学是中医药理论和作用机制阐明的重要研究内容。如何全面、准确地描述中药复杂成分在体内的药代动力学过程，诠释中药多成分、多靶标、多途径的特点，需要强有力的分析技术支撑。近年来，多种高通量、快速、自动化的前处理技术显著提升了中药体内外多成分的分离提取效率；色谱、质谱分析技术蓬勃发展，推动了中药体内外多成分的快速鉴别和全面、准确定量；质谱成像等新兴技术不断涌现，为中药多成分药代动力学研究提供了新的分析平台和研究手段。本文综述了近10年来中药多成分药代动力学研究分析技术的进展和应用，并对其前景进行展望。     

含二硫键多肽的基质辅助激光解吸电离飞行时间质谱研究

The determination of disulfide bonds becomes an important aspect of obtaining a comprehensive understanding of the chemical structure of a protein. Numerous experimental methods have been developed for the determination of disulfide bonds in proteins. Modern mass spectrometry has developed as an important tool for the analysis of disulfide bond patterns due to its advantages of being simple, rapid and sensitive. The dissociations of the disulfide bonds were detected during the matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) analysis. These fragment ions were attributed to prompt fragmentation or “in-source decay” rather than “post-source decay”. For the double disulfide bonds, ions of plus sulfur and minus sulfur atoms corresponding to cleavages at different sites within the carbon-sulfur-sulfur-carbon disulfide bonds were also observed.     

超声雾化萃取大气压光电离质谱法快速分析烟草化学成分

随着烟草工业的发展,对烟草样品进行快速、准确和高灵敏度地分析检测已经成为烟草化学发展的必然趋势和产品研发的现实需求.本工作利用超声雾化萃取大气压光电离质谱(EAPPI-MS)技术,无需样品预处理和色谱分离,对1R5F、3R4F、都宝、七星和王冠5种卷烟烟丝中的化学成分进行直接、快速分析,鉴别出醇、酮、酸、酯、醛、酚、生...     

基质辅助激光解吸电离质谱用于生物组织的质谱成像应用进展

基质辅助激光解吸电离质谱(MALDI MS)用于分析组织切片已成为质谱学的一个新领域。质谱成像技术通过直接对组织切片表面的质谱扫描,可以快速直观地分析组织中的分子,如蛋白质、多肽、药物分子、代谢产物等及其空间分布信息。本工作综述了组织切片的质谱成像原理,方法学和相关应用。     

甲胎蛋白纯品的同位素稀释质谱法测定

建立了基于特征肽段的甲胎蛋白的液相色谱-同位素稀释串联质谱检测方法。选取3条同位素标记的甲胎蛋白特征肽段作为内标,准确称其质量后与酶切后的甲胎蛋白样品定量混合,采取Phenomenex Kinetex 2.6 μm C18色谱柱分离,电喷雾三重四极杆串联质谱多反应监测模式（MRM）测定,并对最优酶切条件、酶切效率以及定值结果的不确定度进行了考察和评定,得到的甲胎蛋白标准物质的最终测量结果为（0.329±0.016）mg/g。     

双（氢化牛脂基）二甲基季铵化合物的质谱裂解规律及色谱分离研究

建立了高效液相色谱-电喷雾串联质谱（HPLC-ESI-MS/MS）联用技术快速鉴定和检测双（氢化牛脂基）二甲基季铵化合物（DHTDMAC）的方法。通过对双（氢化牛脂基）二甲基氯化铵标准品的质谱解析,由一级质谱中各成分的特征母离子峰和二级质谱裂解碎片,得出质谱裂解规律,并推断出标准品中所包含的16种DHTDMAC组分。通过中性丢失扫描、母离子扫描和子离子扫描对质谱解析和裂解规律进行了验证。通过色谱条件的优化,采用电喷雾电离正离子（ESI⁺）、多反应监测（MRM）模式,建立了色谱分离、质谱检测的方法。本研究鉴定出不同链长烷基和碳数的DHTDMAC组分,并建立了DHTDMAC单个组分的简便、高效的检测方法,对准确研究该类化合物,以及加强环境、化工产品和消费品中DHTDMAC的监控提供了依据。     

采用多重离子化方式探讨氨基酸类化合物的离子化效率

Diverse amino acids produce different signal responses with disparate ionization. Accordingly, none of the currently available mass spectrometric techniques can analyze all amino acids simultaneously. Here, it was a better way that combination of electrospray ionization(ESI), atmospheric pressure chemical ionization(APCI) and atmospheric pressure photo ionization(APPI) enhanced ionization efficiency for amino acids. The results show that the application of multiple ionization mass spectrometry is expected to provide a powerful new tool for amino acids research.     

（2,4-二甲氧基苯基）烯丙基丙二酸二乙酯异构体的GC/MS研究

为了研究钯催化的2,4-二甲氧基苯甲酸与烯丙基丙二酸二乙酯的脱羧Heck反应的产物结构,建立了（2,4-二甲氧基苯基）烯丙基丙二酸二乙酯同分异构体的分离与鉴定的气相色谱-离子阱质谱方法。首先通过脱羧Heck反应制得（2,4-二甲氧基苯基）烯丙基丙二酸二乙酯异构体混合物,然后利用GC/MS联用技术对混合物进行分析,得到各组分的EI和CI全扫描模式质谱信息。通过对照各组分的分子离子峰确定互为异构体的组分,再对异构体组分采用MS/MS模式获取各自的裂解碎片。通过分析异构体的不同的裂解碎片,讨论质谱裂解方式,从而确定异构体的结构。该方法省时、经济、高效,可为此类化合物的分析与鉴别提供参考。