DART MS for rapid, preliminary screening of urine for DMAA
DART-MS应用于原尿中的二甲戊胺（DMAA）初步、快速筛查

Ashton D. Lesiak, Kendra J. Adams, Marek A. Domin, Colin Henck, Jason R. E. Shepard
Department of Chemistry, University at Albany, State University of New York (SUNY), Albany, NY; Mass Spectrometry Center, Merkert Chemistry Center, Boston College, Chestnut Hill, MA
Dimethylamylamine (DMAA) is a sympathomimetic amine found in weight-loss/workout supplements or used as an appetite suppressant. DMAA is a stimulant that is banned by the World Anti-Doping Agency (WADA). Adverse health effects as well as fatalities have been implicated with its use. Direct analysis in real time mass spectrometry (DART-MS) is an ambient ionization method that was employed to rapidly identify the presence of DMAA in various samples without any extraction or preparations whatsoever. DMAA was first identified in supplements, sampled directly in their solid forms. Furthermore, DMAA was detected directly in urine over 48 h as a means of indicating recent abuse of the substance. DART-MS analysis is instantaneous, and coupled with the high mass accuracy associated with the time-of-flight mass analyzer, results in unequivocal identification of the presence of DMAA. These features demonstrate DART-MS as an attractive potential alternative screening method for the presence of drugs and medications or for toxicological investigations.

DMAA是一种拟交感神经的胺类药物，通常应用于减肥和抑制食欲。DMAA也是一种兴奋剂，官方机构世界反兴奋剂组织（WADA）严格禁止使用该药物，该药物对身体不仅有副作用甚至可以导致死亡。在没有任何样品萃取以及相关前处理条件下，原位电离技术实时分析串联质谱快速定性鉴别在不同基质中的DMAA。首次发现在营养品中添加的DMAA，直接分析固体样品。此外，超过两天，直接分析原尿，发现含有DMAA，意味着最近滥用该药物。DART串联高分辨质谱，能立即准确定性分析DMAA药物。鉴于DART-MS有诸多优点，表明该分析手段在快速筛查药物以及毒理学等领域有很好的应用前景。

Development of a rapid screening method to determine primary aromatic amines in kitchen utensils using direct analysis in real time mass spectrometry (DART MS)
采用DART-MS分析方法，快速筛查厨具中芳香胺类化合物的残留

Primary aromatic amines (PAAs) are a group of substances with undesirable health effects, that are used in a variety of commercial products. Several recent studies, using a number of screening and confirmatory methods, have reported the migration of PAAs from some kitchen utensils into acetic acid 3% (w/v). Many of these methods require significant sample preparation, therefore the aim of this work was to determine if direct analysis in real time mass spectrometry (DART-MS) could be utilized as a rapid screening tool for the determination of PAAs in kitchen utensils. DART-MS results from direct analysis of the utensil have been compared with results of PAA migration by ultra high performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) method. The UPLC-MS/MS method had excellent linearity, appropriate sensitivity (LOD ≤ 1.5 µg L−1; LOQ ≤ 4.5 µg L−1), repeatability from 2.4 to 13.2% and acceptable recoveries. DART-MS results were in good agreement with UPLC-MS/MS data, with 100% of non-compliant (PAA positive) samples successfully identified by DART-MS.

初级芳香胺类化合物（PAAs）是对身体有害物质，被应用于各种各样的商产品。根据近期的研究报导发现，采用大量的筛查和确准技术，并且样品处理是在厨具上残留PPAs溶解到乙酸（3% W/V）中。诸多方法均需要大量的样品制备过程。因此，本文的目的在于采用实时直接分析离子源串联质谱快速筛查检测厨具表面残留的PAAs类化合物。并且本文比较DART-MS和UPLC-MS/MS的实验结果。UPLC-MS/MS具有良好的线性，高灵敏度（检出限1.5ppb，定量限4.5ppb），高回收率。在正离子模式下，DART-MS实验结果与UPLC-MS/MS一致。

Electro Thermal Vaporization Direct Analysis in Real Time Mass Spectrometry for Water Contaminant Analysis during Space Missions
电热蒸发机制，实时分析离子源串联质谱（DART-MS）分析空间站水中的污染物

The development of a direct analysis in real time-mass spectrometry (DART-MS) method and first prototype vaporizer for the detection of low molecular weight (30-100 Da) contaminants representative of those detected in water samples from the International Space Station is reported. A temperature-programmable, electro-thermal vaporizer (ETV) was designed, constructed, and evaluated as a sampling interface for DART-MS. The ETV facilitates analysis of water samples with minimum user intervention while maximizing analytical sensitivity and sample throughput. The integrated DART-ETV-MS methodology was evaluated in both positive and negative ion modes to (1) determine experimental conditions suitable for coupling DART with ETV as a sample inlet and ionization platform for time-of-flight MS, (2) to identify analyte response ions, (3) to determine the detection limit and dynamic range for target analyte measurement, and (4) to determine the reproducibility of measurements made with the method when using manual sample introduction into the vaporizer. Nitrogen was used as the DART working gas, and the target analytes chosen for the study were ethyl acetate, acetone, acetaldehyde, ethanol, ethylene glycol, dimethylsilanediol, formaldehyde, isopropanol, methanol, methylethyl ketone, methylsulfone, propylene glycol, and trimethylsilanol.

本文首次建立了采用DART-MS分析国际空间水中的污染物质分析方法，该类物质分子量较小，仅仅在30～100Da范围。DART-MS设置了温度控制程序、电热蒸发机制（ETV）、以及设计了串接质谱的接口。该电热蒸发机制技术使得样品尽可能不被干扰，并且很大程上提高灵敏度以及分析通量。DART-ETV-MS方法可以采用正离子模式也可以采用负离子模式：可以与高分辨TOF-MS串接；可以快速定性分析目标物；确定目标物的检出限以及动态分析范围；当采用人工进样时，可以测量重复性。N2作为解析气体，目标物是乙酸乙酯、丙酮、乙醛、乙醇、乙二醇、硅烷二醇二甲酯、甲醛、异丙醇、甲醇、甲基乙基酮、甲基砜、丙二醇三、甲基硅烷等。

On-line coupling of macroporous resin column chromatography with direct analysis in real time mass spectrometry utilizing a surface flowing mode sample holder
采用表面流动进样模式，在线大孔隙的树脂色谱分离技术串联实时分析质谱

A surface flowing mode sample holder was designed as an alternative sampling strategy for direct analysis in real time mass spectrometry (DART-MS). With the sample holder, the on-line coupling of macroporous resin column chromatography with DART-MS was explored and the then achieved through the sample holder. This new hyphenated system was employed to monitor the column chromatography elution process of Panax notoginseng's column chromatography. The effluent from macroporous resin column was first diluted and then mixed with a derivatization reagent on-line, and. After that, the mixture was then directly transferred into the ionization region of DART-MS by the sample holder. Notoginsenosides were methylated and ionized in a metastable helium gas stream, and was introduced then led into MS for the detection. Theis on-line system showed reasonable repeatability with the a relative standard deviations of 12.3% for the peak area. Three notoginsenosides, including i.e. notoginsenoside R1, ginsenoside Rb1 and ginsenoside Rg1, were simultaneously determined during the eluting process. The alteration of the chemical composition in the effluent was rapidly and accurately identified in 9 min, which agreed agreeing well with the off-line analysis determination output. Compared with UPLC method, The presented technique is was more sensitive and convenient compared to the traditional UPLC method. This studyThese results suggested that the surface flowing mode DART-MS could be used for has a good potential for the on-line process monitoring in the pharmaceutical industry.

本文设计了一种非传统的表面流动进样模块作为串联实时分析质谱进样方法。通过固定的取样架，在线的大孔隙色谱分离技术与DART-MS实现串接。这种新的联用系统被用来监控Panax notoginseng色谱柱洗脱过程。来自大孔隙的色谱柱洗脱物与衍生试剂在线相混合，然后混合液被取样架直接取样到电离区域。三七皂甙被甲基化后通过He的亚稳态电离，然后进入质谱。并且该系统有较好的重复性，峰面积相对标准偏差小于12.3%。三七皂甙有三种，包括三七皂苷R1、Rb1、Rg1，在洗脱过程中，被同时检测到。在9分钟之内，在洗脱物中的化学成分组成的变化被快速准确鉴定，实验结果与离线的分析结果一致。与UPLC相比，该方法比传统的UPLC方法更加灵敏、更加简便。研究表明，该方法在医疗制药行业有广阔的应用前景。


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